Nghiên cứu phản ứng của ion amoni NH+4 bằng phương pháp lý thuyết hoá học lượng tử

Mục lục MỞ ĐẦU I. Lý do chọn đề tài . 4 II. Nhiệm vụ và phương pháp nghiên cứu đề tài. 5 II.1. Mục đích của đề tài. 5 II.2. Nhiệm vụ của đề tài. 5 II.3. Phương pháp nghiên cứu đề tài. 5 III. Cấu trúc luận văn. . 6 NỘI DUNG . 7 Chương I: Cơ sở lý thuyết hoá học lượng tử 7 I.1. Phương trình Schrödinger . 7 I.1.1 Toán tử Hamilton 7 I.1.2. Hàm sóng của hệ nhiều electron . 8 I.1.3. Phương trình Schrödinger. 9 I.2. Cấu hình và trạng thái hệ nhiều electron. Bộ hàm cơ sở. . 10 I.2.1. Cấu hình và trạng thái hệ nhiều electron. 10 I.2.2. Bộ hàm cơ sở. 11 I.3. Các phương pháp tính ab-initio trong HHLT. 14 I.3.1. Phương pháp trường tự hợp Hartree-Fock (Hartree-Fock Self Consistent Field) và phương trình Roothaan 14 I.3.2. Phương pháp nhiễu loạn. . 19 I.3.3. Phương pháp biến phân. 21 I.3.4. Phương pháp tương tác cấu hình (Configuration Interaction, CI). . 22 I.3.5. Phương pháp phiếm hàm mật độ (Density Functional Theory, DFT)24 Chương II. Tổng quan hệ chất nghiên cứu và phương pháp nghiên cứu. . 26 II.1 Tổng quan về hệ chất nghiên cứu. 26 II.2 Phương pháp nghiên cứu 27 II.3 Tiến trình nghiên cứu 27 II.4. Ứng dụng lý thuyết HHLT để nghiên cứu các vấn đề Hoá học. 29 II.4.1. Thuyết phức chất hoạt động. . 29 II.4.2. Nguyên tắc axit-bazơ cứng mềm (HSAB principle). 30 II.4.3. Bề mặt thế năng (Potential Energy Surface, PES) 31 II.4.3.1. Khái niệm bề mặt thế năng. . 31 II.4.3.2. Các đặc điểm của bề mặt thế năng . 33 II.4.4. Lý thuyết tính về dung dịch. . 35 Chương III. Kết quả và thảo luận 37 III.1. Phản ứng NH 3 + O 2 → HNO + H 2 O (III.3) 37 III.1.1. Xét phản ứng hướng 1 . 40 III.1.1.1. Giai đoạn 1. . 41 III.1.1.2. Giai đoạn 2. . 42 III.1.1.3. Giai đoạn 3. . 42 III.1.1.4. Giai đoạn 4. . 43 III.1.2. Tính các đại lượng nhiệt động học và động học cho hướng 1 45 III.1.2.1. Tính các đại lượng nhiệt động học 45 III.1.2.2. Tính các đại lượng động học. 46 III.1.3. Xét hướng phản ứng thứ 2 . 47 III.1.4. Tính đại lượng nhiệt động học và động học cho hướng 2 . 50 III.1.5. So sánh hai hướng của phản ứng NH 3 + O 2 → HNO + H 2 O 51 III.2. Phản ứng HNO + + 2 HO → NO + + H 2 O 2 (III.4) . 51 III.2.1. Cơ chế phản ứng. . 53 III.2.2. Tính các đại lượng nhiệt động học 54 III.2.3. Tính các đại lượng động học . 55 III.3. Phản ứng HNO + H 2 O 2 → HONO + H 2 O (III.5) . 56 III.3.1. Cơ chế phản ứng. . 57 III.3.2. Tính các đại lượng nhiệt động học 61 III.3.3. Tính các đại lượng động học . 61 III.4. Nhận xét phản ứng (III.3), (III.4) và (III.5). 62 KẾT LUẬN 64 Tài liệu tham khảo . 66 Phụ lục . 69 I. Phản ứng NH 3 + O 2 → HNO + H 2 O . 69 I.1. Kết quả Scan . 69 I.2. Kết quả tối ưu các TS phản ứng 1. 72 I.3. Kết quả tính tần số 74 I.4. Kết quả chạy IRC phản ứng 1. 77 II. Phản ứng HNO + +2 HO → NO + + H 2 O 2 85 II.1. Các kết quả tối ưu TS phản ứng 2. 85 II.2. Các kết quả chạy IRC phản ứng 2. 86 III. Phản ứng HNO + H 2 O 2 → HONO + H 2 O . 89 III.1. Kết quả Scan IS1 . 89 III.2. Các kết quả tối ưu các TS 91 III.3. Các kết quả tính tần số 93

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2139 1.02574 1.46321 20 -206.80656 1.84445 1.02141 1.02573 1.46390 21 -206.80656 1.85752 1.02142 1.02554 1.46417 22 -206.80656 1.89149 1.02144 1.02569 1.46434 23 -206.80656 1.89460 1.02146 1.02565 1.46445 24 -206.80656 1.91507 1.02145 1.02567 1.46449 …………………………………………………………………………………………………………………………………………………………….. A4 D1 D2 D3 1 89.95012 110.05842 91.66961 -33.54503 2 89.59324 110.08371 93.08089 -34.94197 3 89.13294 110.23925 94.68297 -36.33007 4 88.47164 110.11182 96.11697 -37.75995 5 87.69304 109.89484 97.56410 -39.27046 6 86.85810 109.63506 99.06141 -40.86608 7 85.98756 109.34680 100.61088 -42.53004 8 85.09463 109.04456 102.22342 -44.26783 9 84.19457 108.73673 103.89988 -46.07905 10 83.30096 108.42854 105.63240 -47.95578 11 82.42168 108.12463 107.40746 -49.88429 12 81.56506 107.82972 109.20565 -51.84774 13 80.74323 107.54781 110.99762 -53.82324 14 79.96914 107.28287 112.73992 -55.77711 15 79.26917 107.04126 114.36537 -57.66390 16 78.66931 106.80219 115.78774 -59.44526 17 78.24510 106.57421 117.04520 -61.43470 18 78.08087 106.37406 118.10644 -63.90695 19 78.05727 106.18292 118.86664 -66.20619 20 78.07835 106.07502 119.43960 -67.83261 21 78.06842 106.14371 119.63410 -68.12650 22 78.04580 106.02702 119.73119 -68.59406 23 78.07900 106.03335 119.70612 -68.55177 24 78.05016 106.00774 119.84998 -68.93179 ---------------------------------------------------------------------- TOTAL NUMBER OF GRADIENT CALCULATIONS: 69 TOTAL NUMBER OF POINTS: 23 AVERAGE NUMBER OF GRADIENT CALCULATIONS: 3.00000 ---------------------------------------------------------------------- IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC ------------------------------------------------------------------------ I LOVE THOSE WHO LONG FOR THE IMPOSSIBLE. -- GOETHE Job cpu time: 0 days 1 hours 49 minutes 44.0 seconds. File lengths (MBytes): RWF= 19 Int= 0 D2E= 0 Chk= 11 Scr= 1 Normal termination of Gaussian 98. I.4.4. Với TS2 - IRC forward ******************************************** Gaussian 98: x86-Win32-G98RevA.3 2-Sep-1998 03-Jul-2004 ******************************************** %chk=C:\G98W\Pu_NH3+O2_NH2OH\TS5a\irc_reverse_TS5a-b3lyp %save ---------------------------------------------------------------------- # rb3lyp/6-31++g** scrf=(solvent=Water,a0=3.230000) irc(maxpoint=200,c alcfc,maxcycle=100,reverse) ---------------------------------------------------------------------- chay IRC tu TS- truoc no ------------------------ Symbolic Z-matrix: Charge = 0 Multiplicity = 1 N H 1 B1 Lª Minh Thµnh LuËn v¨n th¹c sÜ khoa häc Ho¸ häc 84 H 1 B2 2 A1 O 1 B3 2 A2 3 D1 0 H 1 B4 2 A3 3 D2 0 O 5 B5 1 A4 2 D3 0 Variables: B1 1.02198 B2 1.02449 B3 1.42095 B4 2.06339 B5 1.38534 A1 106.56753 A2 102.51592 A3 124.7768 A4 89.95012 D1 110.05842 D2 91.66961 D3 -33.54503 IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC # OF POINTS ALONG THE PATH = 33 # OF STEPS = 4 Minimum found on this side of the potential ---------------------------------------------------------------------- SUMMARY OF REACTION PATH FOLLOWING: (Int. Coord: Angstroms, and Degrees) ---------------------------------------------------------------------- ENERGY RX.COORD B1 B2 B3 1 -206.87612 -3.27516 1.01999 1.02099 1.36129 2 -206.87610 -3.19226 1.02010 1.02100 1.36006 3 -206.87602 -3.09385 1.02022 1.02094 1.35871 4 -206.87588 -2.99402 1.02016 1.02070 1.35812 5 -206.87565 -2.89407 1.02021 1.02056 1.35810 6 -206.87533 -2.79411 1.02029 1.02046 1.35845 7 -206.87493 -2.69418 1.02041 1.02035 1.35909 8 -206.87443 -2.59425 1.02055 1.02032 1.35989 9 -206.87386 -2.49435 1.02075 1.02029 1.36085 10 -206.87316 -2.39458 1.02092 1.02039 1.36196 11 -206.87235 -2.29493 1.02114 1.02052 1.36333 12 -206.87136 -2.19535 1.02133 1.02075 1.36495 13 -206.87011 -2.09569 1.02152 1.02102 1.36683 14 -206.86853 -1.99591 1.02166 1.02133 1.36892 15 -206.86654 -1.89604 1.02179 1.02165 1.37118 16 -206.86410 -1.79611 1.02188 1.02196 1.37357 17 -206.86118 -1.69616 1.02195 1.02225 1.37605 18 -206.85778 -1.59620 1.02200 1.02254 1.37862 19 -206.85387 -1.49622 1.02204 1.02280 1.38124 20 -206.84948 -1.39624 1.02206 1.02304 1.38391 21 -206.84461 -1.29627 1.02208 1.02325 1.38661 22 -206.83930 -1.19632 1.02208 1.02342 1.38931 23 -206.83357 -1.09639 1.02207 1.02356 1.39200 24 -206.82748 -0.99647 1.02206 1.02365 1.39463 25 -206.82113 -0.89656 1.02204 1.02371 1.39718 26 -206.81470 -0.79662 1.02200 1.02374 1.39964 27 -206.80846 -0.69667 1.02197 1.02376 1.40202 28 -206.80272 -0.59671 1.02193 1.02378 1.40435 29 -206.79778 -0.49674 1.02188 1.02380 1.40666 30 -206.79381 -0.39677 1.02184 1.02384 1.40900 31 -206.79091 -0.29681 1.02178 1.02388 1.41143 32 -206.78904 -0.19685 1.02184 1.02407 1.41416 33 -206.78809 -0.09756 1.02195 1.02431 1.41775 34 -206.78789 0.00000 1.02198 1.02449 1.42095 ……………………………………………………………………………………………………………………………………………………………………. A4 D1 D2 D3 1 53.18512 121.92477 81.77773 29.68845 2 52.52927 122.10334 82.40293 27.10135 3 52.26437 122.44542 82.93936 24.22321 4 52.38756 122.70637 83.13717 21.95361 5 52.66042 122.84042 83.15391 19.96801 6 53.01854 122.86903 83.04921 18.14712 7 53.45435 122.82528 82.87546 16.40775 8 53.96916 122.65529 82.59829 14.74612 9 54.61795 122.39147 82.27133 13.08809 10 55.51655 121.99009 81.88537 11.35594 11 56.75755 121.49298 81.52916 9.46574 12 58.36648 120.89077 81.21754 7.45546 13 60.28503 120.25748 81.01911 5.35916 Lª Minh Thµnh LuËn v¨n th¹c sÜ khoa häc Ho¸ häc 85 14 62.41881 119.62188 80.93438 3.24637 15 64.68250 119.01372 80.96309 1.14569 16 67.02579 118.43203 81.08081 -0.92563 17 69.41749 117.87866 81.27426 -2.96953 18 71.83711 117.35061 81.53103 -4.99173 19 74.26525 116.84561 81.84352 -7.00008 20 76.67785 116.36125 82.20679 -9.00060 21 79.03970 115.89620 82.61954 -10.99624 22 81.29952 115.45038 83.08377 -12.98441 23 83.39300 115.02492 83.60335 -14.95492 24 85.25683 114.62114 84.18111 -16.89114 25 86.84747 114.23915 84.81696 -18.77632 26 88.15183 113.87664 85.50791 -20.60073 27 89.18162 113.52875 86.24951 -22.36396 28 89.96050 113.18855 87.03662 -24.07197 29 90.50874 112.84740 87.86435 -25.73426 30 90.84472 112.49369 88.72413 -27.35742 31 90.96158 112.11121 89.60465 -28.94800 32 90.89714 111.65084 90.46990 -30.53545 33 90.47878 110.80011 91.00069 -32.07547 34 89.95012 110.05842 91.66961 -33.54503 ---------------------------------------------------------------------- TOTAL NUMBER OF GRADIENT CALCULATIONS: 74 TOTAL NUMBER OF POINTS: 33 AVERAGE NUMBER OF GRADIENT CALCULATIONS: 2.24242 ---------------------------------------------------------------------- IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC ------------------------------------------------------------------------ DISAPPOINTMENT IS THE NURSE OF WISDOM. SIR BOYLE ROCHE Job cpu time: 0 days 1 hours 52 minutes 50.0 seconds. File lengths (MBytes): RWF= 19 Int= 0 D2E= 0 Chk= 11 Scr= 1 Normal termination of Gaussian 98. II. Phản ứng HNO + +2HO → NO + + H2O2 II.1. Các kết quả tối ưu TS phản ứng 2. II.1.1. Tối ưu TS1. ******************************************** Gaussian 98: x86-Win32-G98RevA.3 2-Sep-1998 23-Sep-2004 ******************************************** %chk=C:\G98W\Pu_HNO+HO2+\TS3\B3LYP\opt. %save ---------------------------------------------------------------------- # ub3lyp/6-31g scrf=(solvent=Water,a0=3.25000,dipole) opt(TS,calcfc,noeigentest,maxcycle=100) volume test ---------------------------------------------------------------------- Recommended a0 for SCRF calculation = 3.17 angstrom ( 6.00 bohr) Final structure in terms of initial Z-matrix: N O,1,B1 O,1,B2,2,A1 O,3,B3,1,A2,2,D1,0 H,1,B4,2,A3,3,D2,0 H,4,B5,3,A4,1,D3,0 Variables: B1=1.17789694 B2=1.56238582 B3=1.53509384 B4=1.05193084 B5=1.46224705 A1=116.88544651 A2=107.99432883 A3=130.442592 A4=43.68729132 D1=-8.50858169 D2=171.22631789 D3=-120.28507925 …………………. THE VALUE OF PHILOSOPHY IS, IN FACT, TO BE SOUGHT LARGELY IN ITS VERY UNCERTAINTY. THE MAN WHO HAS NO TINCTURE OF PHILOSOPHY GOES Lª Minh Thµnh LuËn v¨n th¹c sÜ khoa häc Ho¸ häc 86 THROUGH LIFE IMPRISONED IN THE PREJUDICES DERIVED FROM COMMON SENSE, FROM THE HABITUAL BELIEFS OF HIS AGE OR HIS NATION, AND FROM CONVICTIONS WHICH HAVE GROWN UP IN HIS MIND WITHOUT THE CO-OPERATION OR CONSENT OF HIS DELIBERATE REASON. TO SUCH A MAN THE WORLD TENDS TO BE DEFINITE, FINITE, OBVIOUS; COMMON OBJECTS ROUSE NO QUESTIONS, AND UNFAMILIAR POSSIBILITIES ARE CONTEMPTUOUSLY REJECTED. -- BERTRAND RUSSELL Job cpu time: 0 days 0 hours 4 minutes 24.0 seconds. File lengths (MBytes): RWF= 10 Int= 0 D2E= 0 Chk= 6 Scr= 1 Normal termination of Gaussian 98. II.1.2. Tối ưu TS2. ******************************************** Gaussian 98: x86-Win32-G98RevA.3 2-Sep-1998 19-Sep-2004 ******************************************** %chk=C:\G98W\Pu_HNO+HO2+\TS2\B3LYP\qst2 %save ---------------------------------------------------------------------- # rb3lyp/6-31++G** opt(TS,RCFC,noeigentest,maxcycle=100) volume scrf=(solvent=Water,a0=3.10000,dipole) guess=read geom=allcheck test ---------------------------------------------------------------------- Redundant internal coordinates taken from checkpointfile: C:\G98W\Pu_HNO+HO2+\TS2\B3LYP\qst2.chk Charge = 1 Multiplicity = 1 N,0,-1.1678678345,0.2424677826,-0.1458664724 O,0,-1.6748863583,-0.1189183138,0.8277528909 O,0,0.695083944,0.2259382347,-0.6114654101 O,0,1.7656411779,-0.2685204459,0.0913232699 H,0,-0.6937597788,-0.3691763662,-0.9969165401 H,0,2.5821245111,-0.036093913,-0.442904158 Recover connectivity data from disk. Cartesian force constants read from checkpoint file: C:\G98W\Pu_HNO+HO2+\TS2\B3LYP\qst2.chk …………………….. Recommended a0 for SCRF calculation = 3.28 angstrom ( 6.20 bohr) Test job not archived. 1|1|UNPC-UNK|FTS|RB3LYP|6-31G|H2N1O3(1+)|PCUSER|19-Sep-2004|0||# RB3LY P/6-31G OPT(TS,RCFC,NOEIGENTEST,MAXCYCLE=100) SCRF=(SOLVENT=WATER,A0=3 .10000) GUESS=READ GEOM=ALLCHECK VOLUME TEST||Toa do IS gia dinh thu 2 ||1,1|N,-1.1889009833,0.2512342906,-0.1523715878|O,-1.7761202484,-0.13 19436083,0.7742157646|O,0.7293114173,0.2047319035,-0.5413335672|O,1.84 66133456,-0.2373131629,0.0870702213|H,-0.6991401513,-0.3803350525,-0.9 620785843|H,2.6230109187,-0.0621060403,-0.5309396515||Version=x86-Win3 2-G98RevA.3|Dielectric=78.39|A0=3.1|HF=-280.905928|RMSD=5.997e-009|RMS F=9.128e-006|Dipole=0.6006356,-0.2951265,-1.0350288|PG=C01 [X(H2N1O3)] ||@ BE LIKE A POSTAGE STAMP. STICK TO ONE THING UNTIL YOU GET THERE -- JOSH BILLINGS Job cpu time: 0 days 0 hours 34 minutes 36.0 seconds. File lengths (MBytes): RWF= 6 Int= 0 D2E= 0 Chk= 6 Scr= 1 Normal termination of Gaussian 98. II.2. Các kết quả chạy IRC phản ứng 2. II.2.1. Với TS2- reverse ******************************************** Gaussian 98: x86-Win32-G98RevA.3 2-Sep-1998 24-Sep-2004 ******************************************** %chk=C:\G98W\Pu_HNO+HO2+\TS3\B3LYP\freq %save ---------------------------------------------------------------------- # ub3lyp/6-31g guess=read geom=check irc(RCFC,maxpoint=100,maxcycle=10 0,reverse,restart) volume test ---------------------------------------------------------------------- IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC Berny reaction coordinate optimization. Restoring state from the checkpoint file "C:\G98W\Pu_HNO+HO2+\TS3\B3LYP\freq.chk ". Title: %%%%%%%%%%%%%%%%%%%%%%%%%%%%% Lª Minh Thµnh LuËn v¨n th¹c sÜ khoa häc Ho¸ häc 87 Route: # UB3LYP/6-31G GUESS=READ GEOM=CHECK IRC(RCFC,MAXPOINT=100,MAX CYCLE=100,REVERSE) VOLUME TEST Number of steps in this run= 100 maximum allowed number of steps= 100. Search for a local minimum. Pt 13 Step number 70 out of a maximum of 100 ………………………………………………………………………………………………………………………………………………... SUMMARY OF REACTION PATH FOLLOWING: (Int. Coord: Angstroms, and Degrees) ---------------------------------------------------------------------- ENERGY RX.COORD X1 Y1 Z1 1 -280.87685 -1.19244 -1.00247 -0.05399 -0.16809 2 -280.87430 -1.09248 -0.99866 -0.05597 -0.16864 3 -280.87162 -0.99252 -0.99513 -0.05788 -0.16914 4 -280.86883 -0.89256 -0.99184 -0.05970 -0.16958 5 -280.86599 -0.79258 -0.98877 -0.06142 -0.16998 6 -280.86317 -0.69261 -0.98590 -0.06306 -0.17035 7 -280.86043 -0.59262 -0.98321 -0.06460 -0.17069 8 -280.85788 -0.49264 -0.98069 -0.06605 -0.17103 9 -280.85561 -0.39265 -0.97835 -0.06741 -0.17137 10 -280.85373 -0.29266 -0.97618 -0.06871 -0.17171 11 -280.85238 -0.19283 -0.97442 -0.07000 -0.17229 12 -280.85166 -0.09561 -0.97328 -0.07161 -0.17204 13 -280.86367 0.00000 -0.97185 -0.07293 -0.17148 X2 Y2 Z2 X3 Y3 1 -0.98813 -0.06304 1.00992 0.49601 -0.06823 2 -0.98841 -0.06239 1.00968 0.48896 -0.07003 3 -0.98871 -0.06177 1.00949 0.48230 -0.07180 4 -0.98903 -0.06121 1.00932 0.47602 -0.07351 5 -0.98935 -0.06068 1.00918 0.47009 -0.07516 6 -0.98969 -0.06020 1.00905 0.46449 -0.07676 7 -0.99002 -0.05977 1.00893 0.45919 -0.07834 8 -0.99034 -0.05939 1.00881 0.45417 -0.07991 9 -0.99064 -0.05906 1.00868 0.44940 -0.08150 10 -0.99090 -0.05878 1.00853 0.44486 -0.08315 11 -0.99105 -0.05856 1.00834 0.44051 -0.08496 12 -0.99072 -0.05837 1.00720 0.43650 -0.08715 13 -0.99056 -0.05818 1.00618 0.43269 -0.08917 Z3 X4 Y4 Z4 X5 1 -0.84210 1.47657 0.11289 0.23288 -1.76163 2 -0.84394 1.47881 0.11457 0.23416 -1.75847 3 -0.84572 1.48083 0.11627 0.23513 -1.75569 4 -0.84743 1.48263 0.11799 0.23582 -1.75327 5 -0.84903 1.48422 0.11972 0.23623 -1.75117 6 -0.85050 1.48562 0.12146 0.23637 -1.74938 7 -0.85183 1.48684 0.12321 0.23627 -1.74788 8 -0.85300 1.48790 0.12498 0.23594 -1.74667 9 -0.85400 1.48882 0.12676 0.23540 -1.74568 10 -0.85481 1.48966 0.12858 0.23468 -1.74544 11 -0.85540 1.49050 0.13049 0.23383 -1.74392 12 -0.85549 1.49176 0.13260 0.23311 -1.74766 13 -0.85563 1.49260 0.13457 0.23205 -1.75278 Y5 Z5 X6 Y6 Z6 1 -0.32529 -0.83113 0.72306 0.76372 -1.36377 2 -0.31343 -0.83571 0.74768 0.77105 -1.33870 3 -0.30220 -0.83965 0.77423 0.77759 -1.31199 4 -0.29163 -0.84301 0.80229 0.78301 -1.28370 5 -0.28166 -0.84586 0.83158 0.78747 -1.25414 6 -0.27225 -0.84828 0.86187 0.79106 -1.22353 7 -0.26333 -0.85033 0.89297 0.79397 -1.19207 8 -0.25479 -0.85206 0.92473 0.79642 -1.15994 9 -0.24642 -0.85344 0.95700 0.79869 -1.12728 10 -0.23787 -0.85498 0.98949 0.80106 -1.09422 11 -0.22795 -0.85475 1.02160 0.80391 -1.06075 12 -0.21134 -0.85900 1.04793 0.80802 -1.02884 13 -0.19938 -0.86482 1.07796 0.81214 -0.99561 ---------------------------------------------------------------------- TOTAL NUMBER OF GRADIENT CALCULATIONS: 28 TOTAL NUMBER OF POINTS: 12 AVERAGE NUMBER OF GRADIENT CALCULATIONS: 2.33333 ---------------------------------------------------------------------- IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC ------------------------------------------------------------------------ Job cpu time: 0 days 0 hours 34 minutes 47.0 seconds. II.2.2. Với TS2- forward Lª Minh Thµnh LuËn v¨n th¹c sÜ khoa häc Ho¸ häc 88 ******************************************** Gaussian 98: x86-Win32-G98RevA.3 2-Sep-1998 24-Sep-2004 ******************************************** %chk=C:\G98W\Pu_HNO+HO2+\TS3\B3LYP\freq %save ---------------------------------------------------------------------- # ub3lyp/6-31g guess=read geom=check irc(RCFC,maxpoint=100,maxcycle=10 0,forward) volume test ---------------------------------------------------------------------- chay IRC tu TS- truoc --------------------- Redundant internal coordinates taken from checkpointfile: C:\G98W\Pu_HNO+HO2+\TS3\B3LYP\freq.chk Charge = 1 Multiplicity = 1 N,0,-0.9718513873,-0.0729303558,-0.1714802558 O,0,-0.9905641383,-0.0581794678,1.006175657 O,0,0.4326872236,-0.0891682275,-0.8556272281 O,0,1.4925992747,0.1345676454,0.2320500161 H,0,-1.7527815158,-0.1993823101,-0.8648174986 H,0,1.0779623475,0.8121352004,-0.9956082711 Recover connectivity data from disk. IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC Berny reaction coordinate optimization. Cartesian force constants read from checkpoint file: C:\G98W\Pu_HNO+HO2+\TS3\B3LYP\freq.chk SUMMARY OF REACTION PATH FOLLOWING: (Int. Coord: Angstroms, and Degrees) ---------------------------------------------------------------------- ENERGY RX.COORD X1 Y1 Z1 1 -280.86367 0.00000 -0.97185 -0.07293 -0.17148 2 -280.85254 0.09895 -0.97002 -0.07349 -0.17222 3 -280.85450 0.19852 -0.96813 -0.07388 -0.17295 4 -280.85760 0.29851 -0.96622 -0.07436 -0.17319 5 -280.86187 0.39851 -0.96447 -0.07485 -0.17342 6 -280.86728 0.49851 -0.96281 -0.07534 -0.17363 7 -280.87375 0.59851 -0.96124 -0.07580 -0.17385 8 -280.88111 0.69851 -0.95967 -0.07626 -0.17407 9 -280.88912 0.79850 -0.95808 -0.07670 -0.17429 10 -280.89754 0.89850 -0.95643 -0.07714 -0.17451 11 -280.90607 0.99850 -0.95471 -0.07759 -0.17474 12 -280.91444 1.09850 -0.95290 -0.07805 -0.17497 13 -280.92243 1.19849 -0.95094 -0.07853 -0.17521 14 -280.92984 1.29847 -0.94878 -0.07903 -0.17544 15 -280.93658 1.39845 -0.94638 -0.07957 -0.17567 16 -280.94261 1.49843 -0.94368 -0.08016 -0.17590 17 -280.94793 1.59841 -0.94063 -0.08080 -0.17611 18 -280.95256 1.69839 -0.93717 -0.08150 -0.17629 19 -280.95651 1.79836 -0.93320 -0.08229 -0.17644 20 -280.95981 1.89830 -0.92862 -0.08319 -0.17653 21 -280.96250 1.99821 -0.92328 -0.08424 -0.17655 …………………………………………………………………………………………………………………………………………………………… Y5 Z5 X6 Y6 Z6 1 -0.19938 -0.86482 1.07796 0.81214 -0.99561 2 -0.19969 -0.86166 1.11589 0.81483 -0.96258 3 -0.20204 -0.85865 1.15331 0.81745 -0.93134 4 -0.20284 -0.85891 1.19061 0.82060 -0.89892 5 -0.20282 -0.85899 1.22762 0.82391 -0.86603 6 -0.20245 -0.85903 1.26438 0.82718 -0.83275 7 -0.20181 -0.85903 1.30080 0.83024 -0.79897 8 -0.20116 -0.85904 1.33704 0.83311 -0.76498 9 -0.20050 -0.85902 1.37313 0.83582 -0.73085 10 -0.19983 -0.85900 1.40920 0.83858 -0.69675 11 -0.19916 -0.85898 1.44538 0.84162 -0.66291 12 -0.19850 -0.85896 1.48180 0.84516 -0.62949 13 -0.19784 -0.85894 1.51866 0.84962 -0.59687 14 -0.19720 -0.85894 1.55608 0.85535 -0.56541 15 -0.19658 -0.85896 1.59410 0.86249 -0.53537 16 -0.19601 -0.85902 1.63260 0.87091 -0.50687 17 -0.19551 -0.85916 1.67128 0.88004 -0.47966 18 -0.19513 -0.85940 1.70975 0.88910 -0.45336 19 -0.19492 -0.85980 1.74759 0.89729 -0.42767 20 -0.19496 -0.86040 1.78435 0.90388 -0.40252 21 -0.19538 -0.86128 1.81945 0.90825 -0.37822 ---------------------------------------------------------------------- Lª Minh Thµnh LuËn v¨n th¹c sÜ khoa häc Ho¸ häc 89 TOTAL NUMBER OF GRADIENT CALCULATIONS: 38 TOTAL NUMBER OF POINTS: 20 AVERAGE NUMBER OF GRADIENT CALCULATIONS: 1.90000 ---------------------------------------------------------------------- IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC-IRC ------------------------------------------------------------------------ Job cpu time: 0 days 1 hours 13 minutes 21.0 seconds. III. Phản ứng HNO + H2O2 → HONO + H2O III.1. Kết quả Scan IS1 Gaussian 98: x86-Win32-G98RevA.3 2-Sep-1998 13-Oct-2004 ******************************************** %chk=C:\G98W\scan-TS1-2lk-H---N+N---O %save ------------------------------------------------------------------- # rhf/6-31g Scan scrf=(solvent=Water,a0=3.60000) nosymm volume test ------------------------------------------------------------------- Symbolic Z-matrix: Charge = 0 Multiplicity = 1 N O 1 B1 H 1 B2 2 A1 O 1 B3 2 A2 3 D1 0 O 1 B4 2 A3 3 D2 0 H 5 B5 1 A4 2 D3 0 H 4 B6 2 A5 3 D4 0 Variables: B1 1.28097 B2 1.03244 B3 1.80945Scan 20 0.05 B4 2.53374 B5 0.98706 B6 2.1449 Scan 20 -0.05 A1 119.33547 A2 115.77733 A3 133.23536 A4 112.35158 A5 47.63033 D1 103.55735 D2 65.5628 D3 158.99605 D4 -67.21247 Scan the potential surface. Variable Value No. Steps Step-Size -------- ----------- --------- --------- 3 1.809454 20 0.0500 6 2.144895 20 -0.0500 A total of 441 points will be computed. ………………………………………………………………………………………………………………………………………………… Scan completed. Summary of the potential surface scan: N B3 B6 SCF ---- --------- --------- ----------- 1 1.8095 2.1449 -280.36867 2 1.8595 2.1449 -280.36498 3 1.9095 2.1449 -280.36018 4 1.9595 2.1449 -280.35443 5 2.0095 2.1449 -280.34786 6 2.0595 2.1449 -280.34063 7 2.1095 2.1449 -280.33288 8 2.1595 2.1449 -280.32476 9 2.2095 2.1449 -280.31642 10 2.2595 2.1449 -280.30801 11 2.3095 2.1449 -280.29965 12 2.3595 2.1449 -280.29146 13 2.4095 2.1449 -280.28348 14 2.4595 2.1449 -280.27572 15 2.5095 2.1449 -280.26813 Lª Minh Thµnh LuËn v¨n th¹c sÜ khoa häc Ho¸ häc 90 16 2.5595 2.1449 -280.26066 17 2.6095 2.1449 -280.25322 18 2.6595 2.1449 -280.24576 19 2.7095 2.1449 -280.23824 20 2.7595 2.1449 -280.23062 21 2.8095 2.1449 -280.22290 22 1.8095 2.0949 -280.36901 23 1.8595 2.0949 -280.36540 24 1.9095 2.0949 -280.36074 25 1.9595 2.0949 -280.35514 26 2.0095 2.0949 -280.34873 27 2.0595 2.0949 -280.34164 28 2.1095 2.0949 -280.33402 29 2.1595 2.0949 -280.32601 30 2.2095 2.0949 -280.31777 31 2.2595 2.0949 -280.30946 32 2.3095 2.0949 -280.30120 33 2.3595 2.0949 -280.29309 34 2.4095 2.0949 -280.28520 35 2.4595 2.0949 -280.27750 36 2.5095 2.0949 -280.26997 37 2.5595 2.0949 -280.26253 38 2.6095 2.0949 -280.25513 39 2.6595 2.0949 -280.24770 40 2.7095 2.0949 -280.24021 41 2.7595 2.0949 -280.23265 42 2.8095 2.0949 -280.22499 …………………………………………………………. 400 1.8095 1.1949 -280.29099 401 1.8595 1.1949 -280.30659 402 1.9095 1.1949 -280.31887 403 1.9595 1.1949 -280.32864 404 2.0095 1.1949 -280.33646 405 2.0595 1.1949 -280.34273 406 2.1095 1.1949 -280.34773 407 2.1595 1.1949 -280.35164 408 2.2095 1.1949 -280.35461 409 2.2595 1.1949 -280.35673 410 2.3095 1.1949 -280.35810 411 2.3595 1.1949 -280.35876 412 2.4095 1.1949 -280.35880 413 2.4595 1.1949 -280.35824 414 2.5095 1.1949 -280.35714 415 2.5595 1.1949 -280.35554 416 2.6095 1.1949 -280.35348 417 2.6595 1.1949 -280.35099 418 2.7095 1.1949 -280.34811 419 2.7595 1.1949 -280.34486 420 2.8095 1.1949 -280.34127 421 1.8095 1.1449 -280.29076 422 1.8595 1.1449 -280.30726 423 1.9095 1.1449 -280.32058 424 1.9595 1.1449 -280.33143 425 2.0095 1.1449 -280.34029 426 2.0595 1.1449 -280.34751 427 2.1095 1.1449 -280.35334 428 2.1595 1.1449 -280.35796 429 2.2095 1.1449 -280.36152 430 2.2595 1.1449 -280.36413 431 2.3095 1.1449 -280.36588 432 2.3595 1.1449 -280.36687 433 2.4095 1.1449 -280.36715 434 2.4595 1.1449 -280.36679 435 2.5095 1.1449 -280.36585 436 2.5595 1.1449 -280.36438 437 2.6095 1.1449 -280.36242 438 2.6595 1.1449 -280.36002 439 2.7095 1.1449 -280.35720 440 2.7595 1.1449 -280.35401 441 2.8095 1.1449 -280.35047 ---- --------- --------- ----------- In the beginning there was nothing, which exploded. Job cpu time: 0 days 0 hours 22 minutes 35.0 seconds. File lengths (MBytes): RWF= 18 Int= 0 D2E= 0 Chk= 13 Scr= 1 Normal termination of Gaussian 98. Lª Minh Thµnh LuËn v¨n th¹c sÜ khoa häc Ho¸ häc 91 III.2. Các kết quả tối ưu các TS III.2.1. Tối ưu TS1 ******************************************** Gaussian 98: x86-Win32-G98RevA.3 2-Sep-1998 28-Sep-2004 ******************************************** %chk=C:\G98W\Pu_HNO+H2O2\TS3\B3LYP\opt %save ---------------------------------------------------------------------- # rb3lyp/6-31++G*** opt(TS,calcfc,noeigentest,maxcycle=100) scrf=(solvent=Water,a0=3.50000,dipole) volume test ---------------------------------------------------------------------- Recommended a0 for SCRF calculation = 3.26 angstrom ( 6.17 bohr) Test job not archived. 1|1|UNPC-UNK|FTS|RB3LYP|6-31G|H3N1O3|PCUSER|28-Sep-2004|0||# RB3LYP/6- 31G OPT(TS,CALCFC,NOEIGENTEST,MAXCYCLE=100) SCRF=(SOLVENT=WATER,A0=3.5 0000) VOLUME TEST||Toa do chat dang TRANS||0,1|N,0.0536824886,0.632349 1262,0.7643049774|O,0.0913031413,0.5635185281,2.0140668154|H,0.9439444 296,0.6944022823,0.2466584076|O,0.3132365415,-0.2496116306,-1.75335061 25|O,-0.4277278999,-0.9831918727,-0.6819794765|H,-0.4002787145,0.02155 4981,-2.3771230996|H,-0.7339373987,0.2118786553,0.1504360393||Version= x86-Win32-G98RevA.3|Dielectric=78.39|A0=3.5|HF=-281.8954067|RMSD=5.978 e-009|RMSF=2.422e-005|Dipole=-0.2121825,1.098765,-0.621287|PG=C01 [X(H 3N1O3)]||@ What some people mistake for the high cost of living is really the cost of living high. -- Doug Larson Job cpu time: 0 days 0 hours 4 minutes 48.0 seconds. File lengths (MBytes): RWF= 10 Int= 0 D2E= 0 Chk= 6 Scr= 1 Normal termination of Gaussian 98. III.2.2. Tối ưu TS2 ******************************************** Gaussian 98: x86-Win32-G98RevA.3 2-Sep-1998 01-Sep-2004 ******************************************** %chk=C:\G98W\Pu_NH2OH+O2\TS10\B3LYP\opt %save ---------------------------------------------------------------------- # rb3lyp/6-31++g** scrf=(solvent=Water,a0=3.280000,dipole) opt(TS,noeigentest,maxcycle=100) volume ---------------------------------------------------------------------- Recommended a0 for SCRF calculation = 3.31 angstrom ( 6.26 bohr) Final structure in terms of initial Z-matrix: N O,1,B1 H,1,B2,2,A1 H,1,B3,2,A2,3,D1,0 H,2,B4,1,A3,3,D2,0 O,1,B5,2,A4,3,D3,0 O,6,B6,1,A5,2,D4,0 Variables: B1=1.54298517 B2=1.02037156 B3=2.79510173 B4=1.31568967 B5=1.43898083 B6=1.51951102 A1=112.01324823 A2=134.16055672 A3=46.22173775 A4=115.1335302 A5=105.89389069 D1=-169.60768024 D2=-122.27448012 D3=-123.90130259 D4=-98.14272582 …………………………………………………………………………………………. REALITY IS FOR PEOPLE WHO CAN'T FACE SCIENCE FICTION. Lª Minh Thµnh LuËn v¨n th¹c sÜ khoa häc Ho¸ häc 92 Job cpu time: 0 days 0 hours 11 minutes 11.0 seconds. File lengths (MBytes): RWF= 10 Int= 0 D2E= 0 Chk= 6 Scr= 1 Normal termination of Gaussian 98. III.2.3. Tối ưu TS3 ******************************************** Gaussian 98: x86-Win32-G98RevA.3 2-Sep-1998 02-Oct-2004 ******************************************** %chk=C:\G98W\Pu_HNO+H2O2\TS13\B3LYP\opt %save ---------------------------------------------------------------------- # rb3lyp/6-31++g*** guess=read geom=allcheck volume test scrf=(solvent=Water,a0=3.5,dipole)opt(TS,calcfc,noeigentest,maxcycle=100) ---------------------------------------------------------------------- Title Card Required ------------------- Redundant internal coordinates taken from checkpointfile: C:\G98W\Pu_HNO+H2O2\TS13\B3LYP\opt.chk Charge = 0 Multiplicity = 1 N,0,-0.6949731865,0.5662538933,-0.4489599367 O,0,-0.6004210742,0.3730243824,0.8071848192 O,0,0.5135275772,0.4773191939,-1.1262060617 H,0,-1.4831913869,0.1813842767,-0.9809254743 O,0,0.744097456,-1.1055952699,0.7945054851 H,0,0.9702569682,-0.2356352512,-0.4456543349 H,0,0.1201150517,-1.8675127298,0.765425425 Recover connectivity data from disk. …………………………………………………………………………………………………………………………………………………………………………. Recommended a0 for SCRF calculation = 3.17 angstrom ( 5.99 bohr) Test job not archived. 1|1|UNPC-UNK|FTS|RB3LYP|6-31G|H3N1O3|PCUSER|02-Oct-2004|0||# RB3LYP/6- 31G GUESS=READ GEOM=ALLCHECK SCRF=(SOLVENT=WATER,A0=3.50000) OPT(TS,NO EIGENTEST,MAXCYCLE=100) VOLUME TEST||Title Card Required||0,1|N,-0.700 9058651,0.5585311764,-0.4468760975|O,-0.5932539596,0.3663274758,0.8077 67882|O,0.5130045516,0.4974181298,-1.12540909|H,-1.4863847793,0.166303 3076,-0.9780433936|O,0.7453154206,-1.1121995912,0.794507075|H,0.966782 1685,-0.2274998808,-0.4709097983|H,0.1054155648,-1.8608897767,0.762158 9382||Version=x86-Win32-G98RevA.3|Dielectric=78.39|A0=3.5|HF=-281.9136 415|RMSD=5.229e-009|RMSF=4.947e-005|Dipole=-1.3717495,-0.5981455,-0.79 4357|PG=C01 [X(H3N1O3)]||@ Other things may change us, but we start and end with family. -- Anthony Brandt Job cpu time: 0 days 0 hours 11 minutes 20.0 seconds. File lengths (MBytes): RWF= 6 Int= 0 D2E= 0 Chk= 6 Scr= 1 Normal termination of Gaussian 98. III.2.4. Với TS4 ******************************************** Gaussian 98: x86-Win32-G98RevA.3 2-Sep-1998 16-Aug-2004 ******************************************** %chk=C:\G98W\Pu_NH2OH+O2\TS4a\optTS3-b3lyp-lan2 %save ---------------------------------------------------------------------- # rb3lyp/6-31++g** opt(TS,calcfc,noeigentest,maxcycle=100) scrf=(solvent=Water,a0=3.360000,dipole) volume test ---------------------------------------------------------------------- Recommended a0 for SCRF calculation = 3.19 angstrom ( 6.02 bohr) Final structure in terms of initial Z-matrix: N O,1,B1 O,1,B2,2,A1 H,1,B3,2,A2,3,D1,0 O,1,B4,2,A3,3,D2,0 H,1,B5,2,A4,3,D3,0 H,5,B6,1,A5,2,D4,0 Variables: B1=1.30023965 B2=1.30022474 B3=2.40186634 B4=3.40532021 Lª Minh Thµnh LuËn v¨n th¹c sÜ khoa häc Ho¸ häc 93 B5=4.01596062 B6=0.98382932 A1=114.95281815 A2=122.5149378 A3=122.55997824 A4=134.5320745 A5=122.35301892 D1=179.99375399 D2=-179.96769721 D3=-179.9417216 D4=-0.0789653 ……………………………………………………………………………………………………………………….. A MAN BEGINS CUTTING HIS WISDOM TEETH THE 1ST TIME HE BITES OFF MORE THAN HE CAN CHEW. Job cpu time: 0 days 0 hours 14 minutes 8.0 seconds. File lengths (MBytes): RWF= 10 Int= 0 D2E= 0 Chk= 6 Scr= 1 Normal termination of Gaussian 98. III.3. Các kết quả tính tần số III.3.1 Tính tần số TS1. ******************************************** Gaussian 98: x86-Win32-G98RevA.3 2-Sep-1998 13-Oct-2004 ******************************************** %chk=C:\G98W\Pu_HNO+H2O2\TS3\B3LYP\freq %save ---------------------------------------------------------------------- # rb3lyp/6-31++G** geom=allcheck guess=read scrf=(solvent=Water,a0=3.2 50000,dipole) freq test ---------------------------------------------------------------------- 1/10=4,29=7,30=1,38=1,46=1/1,3; 2//2; 3/5=1,6=6,7=1111,11=2,25=1,30=1/1,2,3; 4/5=1,7=1/1; 5/5=2,40=1,42=-5,53=1,56=3250/2; 8/6=4,11=11,23=2/1; 11/6=1,8=1,9=11,15=111,16=11,44=1/1,2,10; 10/6=1,44=1/2; 6/7=2,8=2,9=2,10=2,18=1,28=1/1; 7/8=1,10=1,25=1,44=1/1,2,3,16; 1/10=4,30=1,46=1/3; 99//99; ---------------------- Toa do chat dang TRANS ---------------------- Redundant internal coordinates taken from checkpointfile: C:\G98W\Pu_HNO+H2O2\TS3\B3LYP\freq.chk Charge = 0 Multiplicity = 1 N,0,0.0536824886,0.6323491262,0.7643049774 O,0,0.0913031413,0.5635185281,2.0140668154 H,0,0.9439444296,0.6944022823,0.2466584076 O,0,0.3132365415,-0.2496116306,-1.7533506125 O,0,-0.4277278999,-0.9831918727,-0.6819794765 H,0,-0.4002787145,0.021554981,-2.3771230996 H,0,-0.7339373987,0.2118786553,0.1504360393 Recover connectivity data from disk. GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGrad ……………………………………………………………………. ****** 1 imaginary frequencies (negative Signs) ****** Harmonic frequencies (cm**-1), IR intensities (KM/Mole), Raman scattering activities (A**4/AMU), Raman depolarization ratios, reduced masses (AMU), force constants (mDyne/A) and normal coordinates: 1 2 3 ?A ?A ?A Frequencies -- -882.8470 225.3108 242.8090 Red. masses -- 1.0530 8.0837 4.3472 Frc consts -- 0.4836 0.2418 0.1510 IR Inten -- 99.2874 3.6790 22.5115 Raman Activ -- 0.0000 0.0000 0.0000 Depolar -- 0.0000 0.0000 0.0000 Lª Minh Thµnh LuËn v¨n th¹c sÜ khoa häc Ho¸ häc 94 Atom AN X Y Z X Y Z X Y Z 1 7 0.03 0.03 -0.02 -0.28 -0.10 0.00 0.00 -0.02 0.29 2 8 0.00 0.00 0.00 -0.22 0.16 0.03 0.15 0.08 -0.23 3 1 0.19 0.08 0.08 -0.47 -0.20 -0.02 0.06 -0.37 0.70 4 8 0.00 0.01 0.00 0.50 0.15 0.00 0.01 0.03 -0.15 5 8 0.01 -0.01 -0.03 -0.01 -0.21 -0.04 -0.18 -0.08 0.08 6 1 -0.02 -0.01 0.01 0.26 0.22 0.16 0.14 0.05 -0.23 7 1 -0.59 -0.40 0.66 -0.17 -0.28 -0.01 0.00 0.11 0.21 …………………………………………………………………………………………………………………………………………… ------------------- - Thermochemistry - ------------------- Temperature 298.150 Kelvin. Pressure 1.00000 Atm. Atom 1 has atomic number 7 and mass 14.00307 Atom 2 has atomic number 8 and mass 15.99491 Atom 3 has atomic number 1 and mass 1.00783 Atom 4 has atomic number 8 and mass 15.99491 Atom 5 has atomic number 8 and mass 15.99491 Atom 6 has atomic number 1 and mass 1.00783 Atom 7 has atomic number 1 and mass 1.00783 Molecular mass: 65.01129 amu. Principal axes and moments of inertia in atomic units: 1 2 3 EIGENVALUES -- 67.56672 544.25919 597.48297 X 0.99992 -0.00516 0.01141 Y 0.00493 0.99979 0.01969 Z -0.01151 -0.01963 0.99974 THIS MOLECULE IS AN ASYMMETRIC TOP. ROTATIONAL SYMMETRY NUMBER 1. ROTATIONAL TEMPERATURES (KELVIN) 1.28189 0.15914 0.14496 ROTATIONAL CONSTANTS (GHZ) 26.71050 3.31596 3.02057 1 IMAGINARY FREQUENCIES IGNORED. Zero-point vibrational energy 111617.7 (Joules/Mol) 26.67727 (Kcal/Mol) WARNING-- EXPLICIT CONSIDERATION OF 5 DEGREES OF FREEDOM AS VIBRATIONS MAY CAUSE SIGNIFICANT ERROR VIBRATIONAL TEMPERATURES: 324.17 349.35 429.20 749.71 823.18 (KELVIN) 1061.08 1164.84 1878.89 1908.85 2011.44 2347.78 3792.16 4859.22 5149.02 Zero-point correction= 0.042513 (Hartree/Particle) Thermal correction to Energy= 0.047377 Thermal correction to Enthalpy= 0.048321 Thermal correction to Gibbs Free Energy= 0.015153 Sum of electronic and zero-point Energies= -281.965469 Sum of electronic and thermal Energies= -281.960605 Sum of electronic and thermal Enthalpies= -281.959661 Sum of electronic and thermal Free Energies= -281.992828 E (Thermal) CV S KCAL/MOL CAL/MOL-KELVIN CAL/MOL-KELVIN TOTAL 29.730 15.340 69.807 ELECTRONIC 0.000 0.000 0.000 TRANSLATIONAL 0.889 2.981 38.435 ROTATIONAL 0.889 2.981 24.600 VIBRATIONAL 27.952 9.378 6.773 VIBRATION 1 0.650 1.802 1.916 VIBRATION 2 0.659 1.775 1.782 VIBRATION 3 0.691 1.677 1.426 VIBRATION 4 0.876 1.203 0.607 VIBRATION 5 0.928 1.092 0.500 ……………………………………………………………………. "WOULD YOU TELL ME PLEASE, WHICH WAY I OUGHT TO WALK FROM HERE?" "THAT DEPENDS A GREAT DEAL ON WHERE YOU WANT TO GO," SAID THE CAT. "I DON'T MUCH CARE WHERE -- ", SAID ALICE. "THEN IT DOESN'T MATTER WHICH WAY YOU WALK," SAID THE CAT. -- LEWIS CARROLL Job cpu time: 0 days 0 hours 46 minutes 2.0 seconds. File lengths (MBytes): RWF= 15 Int= 0 D2E= 0 Chk= 6 Scr= 1 Normal termination of Gaussian 98. III.3.2 Tính tần số TS2. ******************************************** Gaussian 98: x86-Win32-G98RevA.3 2-Sep-1998 13-Oct-2004 ******************************************** %chk=C:\G98W\Pu_HNO+H2O2\TS10\B3LYP\freq++ Lª Minh Thµnh LuËn v¨n th¹c sÜ khoa häc Ho¸ häc 95 %save -------------------------------------------------------------------- # rb3lyp/6-31++g** scrf=(solvent=Water,a0=3.310000,dipole) freq test -------------------------------------------------------------------- -------------- Tinh tan so TS -------------- Symbolic Z-matrix: Charge = 0 Multiplicity = 1 N O 1 B1 H 1 B2 2 A1 H 1 B3 2 A2 3 D1 0 H 2 B4 1 A3 3 D2 0 O 1 B5 2 A4 3 D3 0 O 6 B6 1 A5 2 D4 0 Variables: B1 1.54299 B2 1.02037 B3 2.7951 B4 1.31569 B5 1.43898 B6 1.51951 A1 112.01325 A2 134.16056 A3 46.22174 A4 115.13353 A5 105.89389 D1 -169.60768 D2 -122.27448 D3 -123.9013 D4 -98.14273 …………………………………………………………………………………………………………………………………………………… ****** 1 imaginary frequencies (negative Signs) ****** Harmonic frequencies (cm**-1), IR intensities (KM/Mole), Raman scattering activities (A**4/AMU), Raman depolarization ratios, reduced masses (AMU), force constants (mDyne/A) and normal coordinates: 1 2 3 ?A ?A ?A Frequencies -- -1725.1932 215.2199 413.7238 Red. masses -- 1.0908 6.3909 5.7986 Frc consts -- 1.9128 0.1744 0.5848 IR Inten -- 1055.1691 4.5760 0.5603 Raman Activ -- 0.0000 0.0000 0.0000 Depolar -- 0.0000 0.0000 0.0000 Atom AN X Y Z X Y Z X Y Z 1 7 0.05 0.05 0.00 0.03 -0.21 0.04 0.13 -0.06 0.15 2 8 0.02 -0.01 0.03 -0.29 0.21 -0.04 0.31 0.13 -0.09 3 1 -0.03 0.05 -0.12 0.23 -0.23 0.41 0.21 -0.12 0.54 4 1 -0.01 0.00 0.01 0.14 0.44 -0.02 -0.09 0.24 -0.23 5 1 -0.75 -0.46 -0.46 -0.17 -0.26 -0.22 0.32 -0.28 -0.17 6 8 -0.01 0.00 0.00 -0.05 -0.21 -0.08 -0.24 -0.14 -0.16 7 8 0.00 0.00 0.00 0.30 0.19 0.08 -0.21 0.07 0.10 …………………………………………………………………………………………………………………………………………. ------------------- - Thermochemistry - ------------------- Temperature 298.150 Kelvin. Pressure 1.00000 Atm. Atom 1 has atomic number 7 and mass 14.00307 Atom 2 has atomic number 8 and mass 15.99491 Atom 3 has atomic number 1 and mass 1.00783 Atom 4 has atomic number 1 and mass 1.00783 Atom 5 has atomic number 1 and mass 1.00783 Atom 6 has atomic number 8 and mass 15.99491 Atom 7 has atomic number 8 and mass 15.99491 Molecular mass: 65.01129 amu. Principal axes and moments of inertia in atomic units: 1 2 3 EIGENVALUES -- 84.20646 397.73080 428.83599 X 0.99998 -0.00562 -0.00019 Y 0.00562 0.99894 0.04562 Z -0.00007 -0.04562 0.99896 THIS MOLECULE IS AN ASYMMETRIC TOP. ROTATIONAL SYMMETRY NUMBER 1. ROTATIONAL TEMPERATURES (KELVIN) 1.02858 0.21777 0.20197 Lª Minh Thµnh LuËn v¨n th¹c sÜ khoa häc Ho¸ häc 96 ROTATIONAL CONSTANTS (GHZ) 21.43234 4.53759 4.20846 1 IMAGINARY FREQUENCIES IGNORED. Zero-point vibrational energy 107238.6 (Joules/Mol) 25.63064 (Kcal/Mol) WARNING-- EXPLICIT CONSIDERATION OF 5 DEGREES OF FREEDOM AS VIBRATIONS MAY CAUSE SIGNIFICANT ERROR VIBRATIONAL TEMPERATURES: 309.65 595.25 669.01 736.49 860.97 (KELVIN) 949.22 1132.24 1304.60 1549.03 1885.52 1948.67 3717.94 5049.47 5087.46 Zero-point correction= 0.040845 (Hartree/Particle) Thermal correction to Energy= 0.045451 Thermal correction to Enthalpy= 0.046395 Thermal correction to Gibbs Free Energy= 0.013997 Sum of electronic and zero-point Energies= -281.919360 Sum of electronic and thermal Energies= -281.914754 Sum of electronic and thermal Enthalpies= -281.913810 Sum of electronic and thermal Free Energies= -281.946208 E (Thermal) CV S KCAL/MOL CAL/MOL-KELVIN CAL/MOL-KELVIN TOTAL 28.521 15.446 68.186 ELECTRONIC 0.000 0.000 0.000 TRANSLATIONAL 0.889 2.981 38.435 ROTATIONAL 0.889 2.981 24.178 VIBRATIONAL 26.743 9.485 5.574 VIBRATION 1 0.645 1.818 1.999 VIBRATION 2 0.777 1.440 0.914 VIBRATION 3 0.822 1.328 0.752 VIBRATION 4 0.867 1.224 0.629 VIBRATION 5 0.956 1.035 0.452 …………………………………………………………………………………………………………………………………………………………….. COMMON SENSE IS NOT SO COMMON. -- VOLTAIRE Job cpu time: 0 days 0 hours 47 minutes 18.0 seconds. File lengths (MBytes): RWF= 19 Int= 0 D2E= 0 Chk= 6 Scr= 1 Normal termination of Gaussian 98. III.3.3. Tính tần số TS3. ******************************************** Gaussian 98: x86-Win32-G98RevA.3 2-Sep-1998 13-Oct-2004 ******************************************** %chk=C:\G98W\TS13\freq++ %save ------------------------------------------------------------------- # rb3lyp/6-31++g** scrf=(dipole,solvent=Water,a0=3.50000) freq test ------------------------------------------------------------------- -------------- Tinh tan so TS -------------- Symbolic Z-matrix: Charge = 0 Multiplicity = 1 N 0 -0.70091 0.55853 -0.44688 O 0 -0.59325 0.36633 0.80777 O 0 0.513 0.49742 -1.12541 H 0 -1.48638 0.1663 -0.97804 O 0 0.74532 -1.1122 0.79451 H 0 0.96678 -0.2275 -0.47091 H 0 0.10542 -1.86089 0.76216 GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGrad Berny optimization. Initialization pass. Trust Radius=3.00D-01 FncErr=1.00D-07 GrdErr=1.00D-07 Number of steps in this run= 31 maximum allowed number of steps= 100. GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGrad …………………………………………………………………………………………………………………………………………………………… ****** 1 imaginary frequencies (negative Signs) ****** Harmonic frequencies (cm**-1), IR intensities (KM/Mole), Raman scattering activities (A**4/AMU), Raman depolarization ratios, reduced masses (AMU), force constants (mDyne/A) and normal coordinates: 1 2 3 ?A ?A ?A Frequencies -- -601.6312 334.5092 475.4786 Red. masses -- 2.3782 4.1562 3.3632 Lª Minh Thµnh LuËn v¨n th¹c sÜ khoa häc Ho¸ häc 97 Frc consts -- 0.5072 0.2740 0.4480 IR Inten -- 286.7773 271.4484 15.1482 Raman Activ -- 0.0000 0.0000 0.0000 Depolar -- 0.0000 0.0000 0.0000 Atom AN X Y Z X Y Z X Y Z 1 7 -0.02 0.03 0.02 0.05 -0.02 0.03 0.12 -0.04 0.20 2 8 0.15 -0.11 0.00 0.13 -0.05 -0.03 -0.15 0.03 -0.18 3 8 -0.14 -0.07 -0.04 0.18 0.00 -0.01 -0.03 0.07 -0.13 4 1 0.41 -0.19 0.22 0.54 -0.19 0.24 0.59 -0.20 0.40 5 8 0.01 0.17 0.02 -0.39 0.06 -0.01 0.05 -0.08 0.13 6 1 -0.61 -0.39 -0.18 0.37 0.21 0.15 -0.03 0.00 -0.11 7 1 0.13 0.27 -0.05 -0.45 -0.02 0.03 -0.16 0.49 -0.01 ………………………………………………………………………………………………………………………. ------------------- - Thermochemistry - ------------------- Temperature 298.150 Kelvin. Pressure 1.00000 Atm. Atom 1 has atomic number 7 and mass 14.00307 Atom 2 has atomic number 8 and mass 15.99491 Atom 3 has atomic number 8 and mass 15.99491 Atom 4 has atomic number 1 and mass 1.00783 Atom 5 has atomic number 8 and mass 15.99491 Atom 6 has atomic number 1 and mass 1.00783 Atom 7 has atomic number 1 and mass 1.00783 Molecular mass: 65.01129 amu. Principal axes and moments of inertia in atomic units: 1 2 3 EIGENVALUES -- 147.16432 253.35102 370.16354 X 0.99942 -0.03402 0.00326 Y 0.03393 0.99914 0.02393 Z -0.00407 -0.02381 0.99971 THIS MOLECULE IS AN ASYMMETRIC TOP. ROTATIONAL SYMMETRY NUMBER 1. ROTATIONAL TEMPERATURES (KELVIN) 0.58855 0.34187 0.23399 ROTATIONAL CONSTANTS (GHZ) 12.26344 7.12348 4.87552 1 IMAGINARY FREQUENCIES IGNORED. Zero-point vibrational energy 112781.1 (Joules/Mol) 26.95533 (Kcal/Mol) WARNING-- EXPLICIT CONSIDERATION OF 3 DEGREES OF FREEDOM AS VIBRATIONS MAY CAUSE SIGNIFICANT ERROR VIBRATIONAL TEMPERATURES: 481.28 684.10 869.32 962.92 1036.76 (KELVIN) 1191.29 1420.45 1504.81 1779.86 1871.53 2020.50 3201.49 4909.47 5194.97 Zero-point correction= 0.042956 (Hartree/Particle) Thermal correction to Energy= 0.046972 Thermal correction to Enthalpy= 0.047916 Thermal correction to Gibbs Free Energy= 0.016535 Sum of electronic and zero-point Energies= -281.995203 Sum of electronic and thermal Energies= -281.991187 Sum of electronic and thermal Enthalpies= -281.990243 Sum of electronic and thermal Free Energies= -282.021624 E (Thermal) CV S KCAL/MOL CAL/MOL-KELVIN CAL/MOL-KELVIN TOTAL 29.475 13.341 66.046 ELECTRONIC 0.000 0.000 0.000 TRANSLATIONAL 0.889 2.981 38.435 ROTATIONAL 0.889 2.981 24.138 VIBRATIONAL 27.698 7.379 3.473 VIBRATION 1 0.716 1.607 1.238 VIBRATION 2 0.832 1.304 0.722 VIBRATION 3 0.963 1.023 0.442 ……………………………………………………………………………………………………………………………………………………………………….. We're simply so accustomed to the marvels of everyday thought that we never wonder about it. -- Marvin Minsky in "Why people think computers are smart" Job cpu time: 0 days 0 hours 13 minutes 23.0 seconds. File lengths (MBytes): RWF= 19 Int= 0 D2E= 0 Chk= 3 Scr= 1 Normal termination of Gaussian 98. III.3.4. Tính tần số TS4. ******************************************** Gaussian 98: x86-Win32-G98RevA.3 2-Sep-1998 13-Oct-2004 Lª Minh Thµnh LuËn v¨n th¹c sÜ khoa häc Ho¸ häc 98 ******************************************** ------------------------------------------------------------------ # rb3lyp/6-31++g** scrf=(dipole,solvent=Water,a0=3.5000) freq test ------------------------------------------------------------------ 1/10=4,30=1,38=1,46=1/1,3; 2/17=6,18=5/2; 3/5=1,6=6,7=1111,11=2,25=1,30=1/1,2,3; 4/7=1/1; 5/5=2,38=4,40=1,42=-5,53=1,56=3500/2; 8/6=4,11=11,23=2/1; 11/6=1,8=1,9=11,15=111,16=11,44=1/1,2,10; 10/6=1,44=1/2; 6/7=2,8=2,9=2,10=2,18=1,28=1/1; 7/8=1,10=1,25=1,44=1/1,2,3,16; 1/10=4,30=1,46=1/3; 99//99; -------------- Tinh tan so TS -------------- Symbolic Z-matrix: Charge = 0 Multiplicity = 1 N O 1 B1 O 1 B2 2 A1 O 1 B3 2 A2 3 D1 0 H 1 B4 2 A3 3 D2 0 H 4 B5 1 A4 2 D3 0 H 4 B6 1 A5 2 D4 0 Variables: B1 1.34115 B2 1.23289 B3 2.34048 B4 1.44002 B5 0.96914 B6 1.10344 A1 120.7095 A2 74.27108 A3 96.36191 A4 137.11932 A5 58.96357 D1 178.12532 D2 179.18656 D3 106.11723 D4 1.048 GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGrad ……………………………………………………………………………………………………………………………………… ****** 1 imaginary frequencies (negative Signs) ****** Harmonic frequencies (cm**-1), IR intensities (KM/Mole), Raman scattering activities (A**4/AMU), Raman depolarization ratios, reduced masses (AMU), force constants (mDyne/A) and normal coordinates: 1 2 3 ?A ?A ?A Frequencies -- -1275.0218 361.8184 389.2299 Red. masses -- 1.0883 3.0082 4.7460 Frc consts -- 1.0424 0.2320 0.4236 IR Inten -- 9.6899 81.3286 558.5633 Raman Activ -- 0.0000 0.0000 0.0000 Depolar -- 0.0000 0.0000 0.0000 Atom AN X Y Z X Y Z X Y Z 1 7 -0.03 -0.05 0.00 0.01 -0.01 0.33 0.10 0.06 -0.02 2 8 0.04 0.01 0.00 0.00 -0.01 -0.03 0.11 0.16 0.00 3 8 -0.01 0.02 0.00 -0.01 0.01 -0.19 0.23 -0.15 0.00 4 8 -0.01 0.01 0.00 -0.04 0.00 -0.04 -0.35 -0.05 0.03 5 1 0.73 -0.14 0.00 0.06 -0.04 0.42 -0.50 0.01 0.03 6 1 -0.04 -0.07 0.01 0.49 0.08 -0.64 -0.18 -0.15 -0.24 7 1 -0.63 0.22 0.01 0.07 0.02 -0.09 -0.60 0.12 0.06 ……………………………………………………………………………………………………………………………………. ------------------- - Thermochemistry - ------------------- Temperature 298.150 Kelvin. Pressure 1.00000 Atm. Atom 1 has atomic number 7 and mass 14.00307 Atom 2 has atomic number 8 and mass 15.99491 Atom 3 has atomic number 8 and mass 15.99491 Atom 4 has atomic number 8 and mass 15.99491 Lª Minh Thµnh LuËn v¨n th¹c sÜ khoa häc Ho¸ häc 99 Atom 5 has atomic number 1 and mass 1.00783 Atom 6 has atomic number 1 and mass 1.00783 Atom 7 has atomic number 1 and mass 1.00783 Molecular mass: 65.01129 amu. Principal axes and moments of inertia in atomic units: 1 2 3 EIGENVALUES -- 91.24509 405.06002 493.71290 X 0.99983 -0.01464 0.01150 Y 0.01479 0.99981 -0.01275 Z -0.01131 0.01292 0.99985 THIS MOLECULE IS AN ASYMMETRIC TOP. ROTATIONAL SYMMETRY NUMBER 1. ROTATIONAL TEMPERATURES (KELVIN) 0.94924 0.21383 0.17543 ROTATIONAL CONSTANTS (GHZ) 19.77905 4.45549 3.65545 1 IMAGINARY FREQUENCIES IGNORED. Zero-point vibrational energy 105079.7 (Joules/Mol) 25.11466 (Kcal/Mol) WARNING-- EXPLICIT CONSIDERATION OF 4 DEGREES OF FREEDOM AS VIBRATIONS MAY CAUSE SIGNIFICANT ERROR VIBRATIONAL TEMPERATURES: 520.57 560.01 623.82 762.81 1006.06 (KELVIN) 1089.74 1546.68 1630.10 1857.84 1938.56 2209.96 2715.61 3319.29 5495.16 Zero-point correction= 0.040023 (Hartree/Particle) Thermal correction to Energy= 0.044285 Thermal correction to Enthalpy= 0.045229 Thermal correction to Gibbs Free Energy= 0.013328 Sum of electronic and zero-point Energies= -282.080435 Sum of electronic and thermal Energies= -282.076173 Sum of electronic and thermal Enthalpies= -282.075229 Sum of electronic and thermal Free Energies= -282.107129 E (Thermal) CV S KCAL/MOL CAL/MOL-KELVIN CAL/MOL-KELVIN TOTAL 27.789 14.062 67.140 ELECTRONIC 0.000 0.000 0.000 TRANSLATIONAL 0.889 2.981 38.435 ROTATIONAL 0.889 2.981 24.416 VIBRATIONAL 26.012 8.100 4.290 VIBRATION 1 0.736 1.551 1.114 VIBRATION 2 0.757 1.493 1.003 VIBRATION 3 0.794 1.397 0.847 VIBRATION 4 0.885 1.183 0.587 ……………………………………………………………………………………………………………………………………………………….. I (ERNEST RUTHERFORD) CAME INTO THE ROOM, WHICH WAS HALF DARK, AND PRESENTLY SPOTTED LORD KELVIN IN THE AUDIENCE AND REALIZED I WAS IN TROUBLE AT THE LAST PART OF MY SPEECH DEALING THE AGE OF THE EARTH, WHERE MY VIEWS CONFLICTED WITH HIS. TO MY RELIEF KELVIN FELL FAST ASLEEP, BUT AS I CAME TO THE IMPORTANT POINT, I SAW THE OLD BIRD SIT UP AND COCK A BALEFUL GLANCE AT ME! THEN A SUDDEN INSPIRATION CAME AND I SAID LORD KELVIN HAD LIMITED THE AGE OF THE EARTH PROVIDED NO NEW SOURCE WAS DISCOVERED. THAT PROPHETIC UTTERANCE REFERS TO WHAT WE ARE NOW CONSIDERING TONIGHT, RADIUM! BEHOLD! THE OLD BOY BEAMED UPON ME. Job cpu time: 0 days 0 hours 12 minutes 29.0 seconds. File lengths (MBytes): RWF= 19 Int= 0 D2E= 0 Chk= 6 Scr= 1 Normal termination of Gaussian 98.

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