Dear all,
I am investigating an ionization process, the change from CH3CH2COOH NH3 to CH3CH2COO- NH4 in the water.
I used Gaussian with implicit water to optimize geometry to find which state has lower potential. I set the initial conformation to neutral pair and ion pair respectively. With B3LYP/6-31G*, both of them output the neutral pair as results. It seemed Gaussian did not like ion pair.
I added a diffuse function to use B3LYP/6-31+G* for the ion pair. And I got a strange output, which was pretty like a transition state. One N-H bond was around 1.4Angstrom, which should be around 1.04Angstrom for NH3.
Could someone tell me how to tell Gaussian the two molecules in a system should be forced as ions? While the total system has no charge.
The OPT output are attached.
Thanks,
Xiaoquan.
Mr. Sun,
You can use CPHF as well as please pay attention to refs [1 and 2]. Replace "Opt" with "Opt(Redundant,Tight)". Below are shown the input and outputs geometry data with the estimated derivative values along with the calculated frequencies as attachment.
[Ref. 1]. H. Schlegel, Estimating the Hessian for gradient-type geometry optimizations, Theoret. Chim. Acta (Berl.) 66, 333-340 (1984)
[Ref. 2]. C. Peng, P. Azala, H.Schlegel, M. Frisch, Using Redundant Internal Coordinates to Optimize Equilibrium Geometries and Transition States, Journal of Computational Chemistry, Vol. 17, No. 1, 49-56 (1996)
OUTPUT (CH3COOH/NH3)
! Initial Parameters !
! (Angstroms and Degrees) !
! Name Definition Value Derivative Info. !
! R1 R(1,2) 1.5132 estimate D2E/DX2 !
! R2 R(1,5) 1.1136 estimate D2E/DX2 !
! R3 R(1,6) 1.1133 estimate D2E/DX2 !
! R4 R(1,7) 1.1137 estimate D2E/DX2 !
! R5 R(2,3) 1.2081 estimate D2E/DX2 !
! R6 R(2,4) 1.3467 estimate D2E/DX2 !
! R7 R(3,12)1.9849 estimate D2E/DX2 !
! R8 R(4,8) 0.9705 estimate D2E/DX2 !
! R9 R(8,9) 2.1696 estimate D2E/DX2 !
! R10 R(8,12) 2.255 estimate D2E/DX2 !
! R11 R(9,10) 1.0198 estimate D2E/DX2 !
! R12 R(9,11) 1.0196 estimate D2E/DX2 !
! R13 R(9,12) 1.0215 estimate D2E/DX2 !
! A1 A(2,1,5) 110.6284 estimate D2E/DX2 !
! A2 A(2,1,6)110.4305 estimate D2E/DX2 !
! A3 A(2,1,7)110.24 estimate D2E/DX2 !
! A4 A(5,1,6) 108.1179 estimate D2E/DX2 !
! A5 A(5,1,7) 109.1791 estimate D2E/DX2 !
! A6 A(6,1,7) 108.1783 estimate D2E/DX2 !
! A7 A(1,2,3) 126.3052 estimate D2E/DX2 !
! A8 A(1,2,4) 111.2607 estimate D2E/DX2 !
! A9 A(3,2,4) 122.4334 estimate D2E/DX2 !
! A10 A(2,4,8) 106.8339 estimate D2E/DX2 !
! A11 A(10,9,11) 104.5008 estimate D2E/DX2 !
! A12 A(10,9,12) 104.4997 estimate D2E/DX2 !
! A13 A(11,9,12) 104.5004 estimate D2E/DX2 !
! D1 D(5,1,2,3) 124.3115 estimate D2E/DX2 !
! D2 D(5,1,2,4) -55.9901 estimate D2E/DX2 !
! D3 D(6,1,2,3) 4.6545 estimate D2E/DX2 !
! D4 D(6,1,2,4) -175.6471 estimate D2E/DX2 !
! D5 D(7,1,2,3) -114.8292 estimate D2E/DX2 !
! D6 D(7,1,2,4) 64.8692 estimate D2E/DX2 !
! D7 D(1,2,4,8) -179.114 estimate D2E/DX2 !
! D8 D(3,2,4,8) 0.5979 estimate D2E/DX2 !
----------------
----------------------------
! Optimized Parameters !
! (Angstroms and Degrees) !
! Name Definition Value Derivative Info. !
-------------------------------------------------------------
! R1 R(1,2) 1.5092 -DE/DX = 0. !
! R2 R(1,5) 1.092 -DE/DX = 0.0002 !
! R3 R(1,6) 1.0899 -DE/DX = 0.0001 !
! R4 R(1,7) 1.0962 -DE/DX = 0.0001 !
! R5 R(2,3) 1.2238 -DE/DX = 0. !
! R6 R(2,4) 1.3382 -DE/DX = -0.0001 !
! R7 R(3,12)2.3929 -DE/DX = 0.0002 !
! R8 R(4,8) 1.0098 -DE/DX = -0.0004 !
! R9 R(8,9) 1.739 -DE/DX = 0. !
! R10 R(8,12)2.0641 -DE/DX = 0. !
! R11 R(9,10)1.017 -DE/DX = -0.0001 !
! R12 R(9,11)1.0159 -DE/DX = 0. !
! R13 R(9,12)1.0204 -DE/DX = -0.0002 !
! A1 A(2,1,5) 111.3027 -DE/DX = 0. !
! A2 A(2,1,6)110.1132 -DE/DX = 0. !
! A3 A(2,1,7) 107.924 -DE/DX = 0.0001 !
! A4 A(5,1,6)111.0473 -DE/DX = 0. !
! A5 A(5,1,7) 107.5882 -DE/DX = -0.0001 !
! A6 A(6,1,7) 108.7464 -DE/DX = 0. !
! A7 A(1,2,3) 123.8485 -DE/DX = 0. !
! A8 A(1,2,4) 112.6404 -DE/DX = 0.0001 !
! A9 A(3,2,4)123.4666 -DE/DX = -0.0001 !
! A10 A(2,4,8) 108.6506 -DE/DX = 0.0001 !
! A11 A(10,9,11) 108.0629 -DE/DX = 0. !
! A12 A(10,9,12)108.3812 -DE/DX = 0. !
! A13 A(11,9,12) 108.7717 -DE/DX = -0.0001 !
! D1 D(5,1,2,3) 143.592 -DE/DX = 0. !
! D2 D(5,1,2,4) -38.7657 -DE/DX = 0. !
! D3 D(6,1,2,3) 19.9976 -DE/DX = 0. !
! D4 D(6,1,2,4) -162.3601 -DE/DX = 0.0001 !
! D5 D(7,1,2,3) -98.5679 -DE/DX = -0.0001 !
! D6 D(7,1,2,4) 79.0744 -DE/DX = 0. !
! D7 D(1,2,4,8) -169.0344 -DE/DX = -0.0001 !
! D8 D(3,2,4,8) 8.6183 -DE/DX = -0.0001 !
-----------------------------------------------------------------------------
INPUT (CH3COO-/NH4+)
#P B3LYP/6-31+G(d,p)
# Opt(Redundant,Tight)
# freq
# Gfinput IOP(6/7=3) Pop=full Density Test
# Units(Ang,Deg)
0 1
C -1 -2.166118 -0.209142 0.003001
C -1 -0.683608 0.072186 -0.002165
O -1 -0.057980 1.215460 0.000671
O -1 0.211560 -0.879515 -0.002059
H -1 -2.429941 -0.825074 -0.885769
H -1 -2.726256 0.751731 -0.042750
H -1 -2.433883 -0.771070 0.925768
N -1 2.126903 -0.094888 0.000716
H -1 1.620672 0.212316 -0.860753
H -1 1.608469 0.185840 0.863969
H -1 3.060854 0.373542 0.014763
H -1 2.281485 -1.128892 -0.014157
OUTPUT (CH3COO-/NH4+)
Default route: MaxDisk=2000MB
----------------------------------------------------------------------
#P B3LYP/6-31+G(d,p) # Opt(Redundant,Tight) # freq # Gfinput IOP(6/7=3
) Pop=full Density Test # Units(Ang,Deg)
----------------------------------------------------------------------
1/7=10,14=-1,18=20,26=3,38=1/1,3;
2/9=110,17=6,18=5/2;
3/5=1,6=6,7=111,11=2,24=10,25=1,30=1/1,2,3;
4//1;
5/5=2,38=4,42=-5/2;
6/7=3,22=-1,28=1/1;
7//1,2,3,16;
1/14=-1,18=20/3(1);
99//99;
2/9=110/2;
3/5=1,6=6,7=111,11=2,25=1,30=1/1,2,3;
4/5=5,16=2/1;
5/5=2,38=4,42=-5/2;
7//1,2,3,16;
1/14=-1,18=20/3(-5);
2/9=110/2;
6/7=3,19=2,22=-1,28=1/1;
99/9=1/99;
.............
----------------------------
! Initial Parameters !
! (Angstroms and Degrees) !
------------------------ -------------------------
! Name Definition Value Derivative Info. !
-----------------------------------------------------------------------------
! X1 R(1,-1)-2.1661 Frozen
! Y1 R(1,-2)-0.2091 Frozen !
! Z1 R(1,-3)0.003 Frozen !
! X2 R(2,-1)-0.6836 Frozen !
! Y2 R(2,-2)0.0722 Frozen !
! Z2 R(2,-3)-0.0022 Frozen !
! X3 R(3,-1)-0.058 Frozen !
! Y3 R(3,-2)1.2155 Frozen !
! Z3 R(3,-3)0.0007 Frozen !
! X4 R(4,-1)0.2116 Frozen !
! Y4 R(4,-2)-0.8795 Frozen !
! Z4 R(4,-3)-0.0021 Frozen !
! X5 R(5,-1) -2.4299 Frozen !
! Y5 R(5,-2) -0.8251 Frozen !
! Z5 R(5,-3) -0.8858 Frozen !
! X6 R(6,-1) -2.7263 Frozen !
! Y6 R(6,-2) 0.7517 Frozen !
! Z6 R(6,-3) -0.0428 Frozen !
! X7 R(7,-1) -2.4339 Frozen !
! Y7 R(7,-2) -0.7711 Frozen !
! Z7 R(7,-3) 0.9258 Frozen !
! X8 R(8,-1) 2.1269 Frozen !
! Y8 R(8,-2) -0.0949 Frozen !
! Z8 R(8,-3) 0.0007 Frozen !
! X9 R(9,-1) 1.6207 Frozen !
! Y9 R(9,-2) 0.2123 Frozen !
! Z9 R(9,-3) -0.8608 Frozen !
! X10 R(10,-1) 1.6085 Frozen !
! Y10 R(10,-2) 0.1858 Frozen !
! Z10 R(10,-3) 0.864 Frozen !
! X11 R(11,-1) 3.0609 Frozen !
! Y11 R(11,-2) 0.3735 Frozen !
! Z11 R(11,-3) 0.0148 Frozen !
! X12 R(12,-1) 2.2815 Frozen !
! Y12 R(12,-2) -1.1289 Frozen !
! Z12 R(12,-3) -0.0142 Frozen !
-----------------------------------------------------------------------------
.............
Predicted change in Energy=-9.032973D-33
Optimization completed.
-- Stationary point found.
----------------------------
! Optimized Parameters !
! (Angstroms and Degrees) !
------------------------ -------------------------
! Name Definition Value Derivative Info. !
-----------------------------------------------------------------------------
! X1 R(1,-1) -2.1661 -DE/DX = -0.0073 !
! Y1 R(1,-2) -0.2091 -DE/DX = 0.0113 !
! Z1 R(1,-3) 0.003 -DE/DX = -0.0023 !
! X2 R(2,-1) -0.6836 -DE/DX = 0.0997 !
! Y2 R(2,-2) 0.0722 -DE/DX = 0.0084 !
! Z2 R(2,-3) -0.0022 -DE/DX = 0.0007 !
! X3 R(3,-1) -0.058 -DE/DX = -0.0638 !
! Y3 R(3,-2) 1.2155 -DE/DX = 0.0096 !
! Z3 R(3,-3) 0.0007 -DE/DX = -0.0004 !
! X4 R(4,-1) 0.2116 -DE/DX = -0.0969 !
! Y4 R(4,-2) -0.8795 -DE/DX = -0.0505 !
! Z4 R(4,-3) -0.0021 -DE/DX = -0.0004 !
! X5 R(5,-1) -2.4299 -DE/DX = 0.0036 !
! Y5 R(5,-2) -0.8251 -DE/DX = 0.0048 !
! Z5 R(5,-3) -0.8858 -DE/DX = 0.0109 !
! X6 R(6,-1) -2.7263 -DE/DX = 0.0044 !
! Y6 R(6,-2) 0.7517 -DE/DX = -0.0119 !
! Z6 R(6,-3) -0.0427 -DE/DX = 0.0021 !
! X7 R(7,-1) -2.4339 -DE/DX = 0.0027 !
! Y7 R(7,-2) -0.7711 -DE/DX = 0.0055 !
! Z7 R(7,-3) 0.9258 -DE/DX = -0.0109 !
! X8 R(8,-1) 2.1269 -DE/DX = 0.0679 !
! Y8 R(8,-2) -0.0949 -DE/DX = 0.0121 !
! Z8 R(8,-3) 0.0007 -DE/DX = 0.0004 !
! X9 R(9,-1) 1.6207 -DE/DX = -0.0001 !
! Y9 R(9,-2) 0.2123 -DE/DX = -0.0032 !
! Z9 R(9,-3) -0.8608 -DE/DX = 0.0272 !
! X10 R(10,-1) 1.6085 -DE/DX = 0.0005 !
! Y10 R(10,-2) 0.1858 -DE/DX = -0.0029 !
! Z10 R(10,-3) 0.864 -DE/DX = -0.0274 !
! X11 R(11,-1) 3.0609 -DE/DX = -0.0019 !
! Y11 R(11,-2) 0.3735 -DE/DX = -0.0032 !
! Z11 R(11,-3) 0.0148 -DE/DX = -0.0004 !
! X12 R(12,-1) 2.2815 -DE/DX = -0.0089 !
! Y12 R(12,-2) -1.1289 -DE/DX = 0.0202 !
! Z12 R(12,-3) -0.0142 -DE/DX = 0.0004 !
-----------------------------------------------------------------------------
GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGrad
Dr. Ivanova, thanks very much for your taking time to give me the detailed example.
Additional data to the topic of the question, relating the monitoring of the optimization procedure of acid/base interaction with
spontaneous H-transfer
Initial geometry (Initial state 1, attachment)
----------------------------
! Initial Parameters !
! (Angstroms and Degrees) !
------------------------ -------------------------
! Name Definition Value Derivative Info. !
-----------------------------------------------------------------------------
! R1 R(1,2) 1.5089 estimate D2E/DX2 !
! R2 R(1,5) 1.1131 estimate D2E/DX2 !
! R3 R(1,6) 1.1131 estimate D2E/DX2 !
! R4 R(1,7) 1.1132 estimate D2E/DX2 !
! R5 R(2,3) 1.2442 estimate D2E/DX2 !
! R6 R(2,4) 1.4943 estimate D2E/DX2 !
! R7 R(2,11) 2.4592 estimate D2E/DX2 !
! R8 R(2,12) 2.4359 estimate D2E/DX2 !
! R9 R(3,11) 2.2019 estimate D2E/DX2 !
! R10 R(3,12) 2.1944 estimate D2E/DX2 !
! R11 R(4,8) 2.0182 estimate D2E/DX2 !
! R12 R(4,10) 1.9561 estimate D2E/DX2 !
! R13 R(4,11) 1.9678 estimate D2E/DX2 !
! R14 R(4,12) 1.9626 estimate D2E/DX2 !
! R15 R(8,9) 1.0448 estimate D2E/DX2 !
! R16 R(8,10) 1.0456 estimate D2E/DX2 !
! R17 R(8,11) 1.0455 estimate D2E/DX2 !
! R18 R(8,12) 1.0454 estimate D2E/DX2 !
! A1 A(2,1,5) 109.8598 estimate D2E/DX2 !
! A2 A(2,1,6) 110.8832 estimate D2E/DX2 !
! A3 A(2,1,7) 109.6561 estimate D2E/DX2 !
! A4 A(5,1,6) 108.7598 estimate D2E/DX2 !
! A5 A(5,1,7) 108.9646 estimate D2E/DX2 !
! A6 A(6,1,7) 108.679 estimate D2E/DX2 !
! A7 A(1,2,3) 125.8152 estimate D2E/DX2 !
! A8 A(1,2,4) 122.1288 estimate D2E/DX2 !
! A9 A(3,2,4) 112.0518 estimate D2E/DX2 !
! A10 A(9,8,10) 108.2121 estimate D2E/DX2 !
! A11 A(9,8,11) 108.1786 estimate D2E/DX2 !
! A12 A(9,8,12) 108.1254 estimate D2E/DX2 !
! A13 A(10,8,11) 110.487 estimate D2E/DX2 !
! A14 A(10,8,12) 110.4933 estimate D2E/DX2 !
! A15 A(11,8,12) 111.2346 estimate D2E/DX2 !
! D1 D(5,1,2,3) 115.8818 estimate D2E/DX2 !
! D2 D(5,1,2,4) -64.9225 estimate D2E/DX2 !
! D3 D(6,1,2,3) -4.3691 estimate D2E/DX2 !
! D4 D(6,1,2,4) 174.8266 estimate D2E/DX2 !
! D5 D(7,1,2,3) -124.387 estimate D2E/DX2 !
! D6 D(7,1,2,4) 54.8087 estimate D2E/DX2 !
-----------------------------------------------------------------------------
Intermediate state (State 2, attachment)
Variable Old X -DE/DX Delta X Delta X Delta X New X
(DIIS) (GDIIS) (Total)
R1 2.89684 -0.00227 0.00000 -0.00632 -0.00632 2.89052
R2 2.07081 -0.00014 0.00000 -0.00002 -0.00002 2.07080
R3 2.06081 0.00044 0.00000 0.00047 0.00047 2.06128
R4 2.06887 -0.00002 0.00000 0.00062 0.00062 2.06949
R5 2.40494 -0.00120 0.00000 0.00122 0.00123 2.40617
R6 2.38780 0.00974 0.00000 0.01978 0.01968 2.40748
R7 4.61402 0.00278 0.00000 0.10032 0.09972 4.71375
R8 4.60230 0.00185 0.00000 0.04952 0.04902 4.65132
R9 4.09450 -0.00251 0.00000 -0.08610 -0.08574 4.00875
R10 4.04609 -0.00280 0.00000 -0.10244 -0.10214 3.94395
R11 4.63307 0.00011 0.00000 0.12094 0.12043 4.75350
R12 4.01188 0.00058 0.00000 0.03224 0.03245 4.04433
R13 4.24445 0.00356 0.00000 0.17350 0.17404 4.41848
R14 4.22915 0.00434 0.00000 0.19425 0.19472 4.42387
R15 1.92468 0.00227 0.00000 0.00229 0.00229 1.92697
R16 1.93695 -0.00036 0.00000 0.00243 0.00247 1.93941
R17 1.95126 -0.00107 0.00000 0.00172 0.00167 1.95293
R18 1.95281 -0.00081 0.00000 0.00303 0.00298 1.95579
A1 1.91075 -0.00038 0.00000 -0.00264 -0.00264 1.90811
A2 1.94308 -0.00024 0.00000 -0.00628 -0.00629 1.93679
A3 1.90739 0.00036 0.00000 0.00253 0.00253 1.90993
A4 1.91292 0.00019 0.00000 0.00330 0.00329 1.91621
A5 1.86306 0.00029 0.00000 0.00229 0.00229 1.86535
A6 1.92488 -0.00020 0.00000 0.00114 0.00114 1.92601
A7 2.05766 0.00134 0.00000 0.00738 0.00740 2.06506
A8 2.04930 0.00025 0.00000 0.00780 0.00781 2.05711
A9 2.17614 -0.00158 0.00000 -0.01448 -0.01594 2.16019
A10 2.04956 -0.00182 0.00000 -0.01142 -0.01128 2.03828
A11 2.01732 -0.00106 0.00000 -0.00822 -0.00810 2.00923
A12 2.02019 -0.00107 0.00000 -0.00759 -0.00746 2.01272
A13 1.82351 0.00190 0.00000 0.01639 0.01618 1.83968
A14 1.82257 0.00186 0.00000 0.01575 0.01555 1.83811
A15 1.68376 0.00110 0.00000 0.00042 0.00019 1.68395
D1 2.05444 -0.00076 0.00000 -0.02745 -0.02744 2.02700
D2 -1.10033 0.00046 0.00000 0.02756 0.02756 -1.07276
D3 -0.06337 -0.00059 0.00000 -0.02572 -0.02573 -0.08909
D4 3.06505 0.00064 0.00000 0.02928 0.02927 3.09433
D5 -2.19393 -0.00043 0.00000 -0.02475 -0.02475 -2.21868
D6 0.93449 0.00080 0.00000 0.03026 0.03026 0.96474
Intermediate state (State 3, attachment) - H-transfer
Variable Old X -DE/DX Delta X Delta X Delta X New X
(DIIS) (GDIIS) (Total)
R1 2.86915 0.00436 0.00243 -0.00267 -0.00024 2.86891
R2 2.07400 -0.00105 -0.00053 -0.00060 -0.00113 2.07287
R3 2.06549 -0.00111 -0.00001 0.00050 0.00049 2.06598
R4 2.07223 -0.00142 -0.00046 -0.00038 -0.00084 2.07139
R5 2.40919 -0.00656 -0.00836 -0.02994 -0.03653 2.37266
R6 2.42352 -0.00757 0.00425 0.02420 0.02677 2.45029
R7 5.33057 0.00480 0.01831 0.28207 0.30234 5.63290
R8 4.90025 0.00548 -0.00836 -0.00141 -0.01986 4.88040
R9 4.57082 0.00169 0.08546 0.56699 0.65100 5.22183
R10 3.56531 -0.00512 0.03915 0.02901 0.07413 3.63944
R11 5.01855 -0.00435 -0.06049 -0.21725 -0.28945 4.72910
R12 3.27463 -0.00650 -0.06026 -0.53292 -0.58519 2.68944
R13 5.23796 0.00027 -0.04163 0.06253 0.02151 5.25947
R14 5.22393 -0.00382 -0.08355 -0.06557 -0.14114 5.08279
R15 1.93605 -0.00565 -0.00095 -0.00067 -0.00162 1.93443
R16 2.00696 0.00790 0.01074 0.06298 0.08139 2.08834
R17 1.92714 0.00184 -0.00361 -0.01853 -0.02252 1.90462
R18 1.98473 -0.00532 -0.00083 -0.00216 -0.00360 1.98113
A1 1.91702 0.00047 0.00112 0.00575 0.00686 1.92387
A2 1.94748 -0.00120 0.00032 0.00044 0.00076 1.94824
A3 1.90737 0.00004 0.00076 0.00031 0.00106 1.90843
A4 1.90529 0.00050 -0.00064 -0.00326 -0.00390 1.90138
A5 1.87006 -0.00049 -0.00105 -0.00040 -0.00146 1.86861
A6 1.91502 0.00071 -0.00057 -0.00287 -0.00344 1.91157
A7 2.04238 0.00477 0.00975 0.02052 0.03379 2.07617
A8 2.02061 0.00285 0.00167 -0.01461 -0.00941 2.01119
A9 2.21772 -0.00715 -0.01134 -0.00741 -0.02596 2.19177
A10 2.02735 0.00272 -0.00039 0.00897 0.00908 2.03643
A11 2.02806 -0.00477 -0.01096 -0.02684 -0.03724 1.99082
A12 2.11549 -0.00580 -0.00139 0.02574 0.02494 2.14043
A13 1.74896 0.00520 -0.00119 -0.03361 -0.03710 1.71187
A14 1.74995 0.00061 -0.00219 -0.06053 -0.06700 1.68295
A15 1.73243 0.00434 0.01893 0.08119 0.10066 1.83309
D1 2.07022 -0.00282 -0.00026 0.00841 0.00826 2.07848
D2 -1.14156 0.00335 0.00044 -0.01322 -0.01288 -1.15445
D3 -0.04510 -0.00298 -0.00043 0.00832 0.00800 -0.03710
D4 3.02630 0.00319 0.00027 -0.01331 -0.01314 3.01316
D5 -2.16612 -0.00311 -0.00044 0.01144 0.01111 -2.15500
D6 0.90528 0.00306 0.00027 -0.01019 -0.01003 0.89525
...........................................................................
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