6 -.081153 1.087175 .000001 6 1.228511 .438669 .000009 7 1.362107 -.825243 -.000160 1 2.322337 -1.112699 -.000124 1 2.087366 1.102717 .000222 1 -.130750 2.159292 .000047 6 -1.227768 .386426 .000152 8 -1.336503 -.927172 .000000 1 -2.182122 .885400 .000317 1 -.457092 -1.314248 -.000321
6 -0.114408 1.135095 0.000022 6 1.152199 0.495995 -0.000019 7 1.217883 -0.797839 -0.000041 1 2.120367 -1.220643 -0.000069 1 2.054780 1.092239 -0.000032 1 -0.207234 2.202118 0.000038 6 -1.224421 0.307495 0.000032 8 -1.146373 -0.958767 0.000012 1 -2.220367 0.734677 0.000063 1 0.018036 -1.184895 -0.000018
6 .124882 1.079430 -.000078 6 -1.124577 .545691 -.000092 7 -1.435476 -.759313 -.000017 1 -2.382123 -1.052279 .000585 1 -.698670 -1.430661 .000651 1 -1.971856 1.212279 -.000226 1 .233095 2.147346 .000230 6 1.319033 .254797 .000071 1 2.266561 .803351 .000811 8 1.335662 -.955544 -.000167
So
/
B3LYP/Enol6 0.000000 1.126958 0.000000 6 1.233831 0.375869 0.000000 7 1.219050 -0.929703 0.000000 1 2.149385 -1.345844 0.000000 1 2.172779 0.944367 0.000000 1 0.019377 2.211069 0.000000 6 -1.202219 0.461655 0.000000 8 -1.318721 -0.857393 0.000000 1 -2.155874 0.992060 0.000000 1 -0.358917 -1.221483 0.000000
TS
6 .103157 1.141103 -.000020 6 -1.169837 .499781 .000020 7 -1.230737 -.816163 .000041 1 -2.157116 -1.231568 .000070 1 -2.081426 1.105990 .000031 1 .189764 2.221026 -.000039 6 1.234422 .327826 -.000034 8 1.173256 -.970110 -.000012 1 2.240106 .762998 -.000064 1 .031336 -1.196689 .000018
Keto
6 -.074957 1.112869 .000118 6 1.230303 .456269 .000015 7 1.323586 -.842747 -.000133 1 2.294124 -1.152118 -.000186 1 2.114437 1.101427 .000070 1 -.129549 2.194107 .000227 6 -1.233589 .390939 .000076 8 -1.311051 -.949078 -.000058 1 -2.208100 .871626 .000151 1 -.378151 -1.283656 -.000115
6 .115506 1.145713 -.000021 6 -1.164069 .515809 .000018 7 -1.225325 -.802942 .000040 1 -2.145200 -1.224775 .000068 1 -2.076038 1.114301 .000029 1 .214377 2.222015 -.000040 6 1.235845 .312554 -.000033 8 1.155327 -.985177 -.000010 1 2.243268 .736682 -.000062 1 -.025435 -1.190667 .000020
6 .125511 1.102329 .000049 6 -1.138022 .555095 -.000206 7 -1.409321 -.774581 -.000591 1 -2.357061 -1.106997 .000506 1 -.625607 -1.416275 -.000063 1 -2.009506 1.205501 -.000171 1 .232489 2.180066 -.000330 6 1.316895 .268880 .000742 1 2.281583 .808201 -.000130 8 1.314631 -.975782 .000102
So/CASSCF/Enol
6 -0.055641 1.109784 0.000000 6 1.270642 0.479191 0.000000 6 -1.218449 0.419141 0.000000 7 1.416315 -0.817730 0.000000 1 2.387843 -1.074011 0.000000 1 2.124816 1.145636 0.000000 1 -0.105483 2.182847 0.000000 1 -2.165625 0.928637 0.000000 1 -0.483311 -1.312173 0.000000 8 -1.348140 -0.908554 0.000000
TS
6 0.163018 1.156178 0.000000 6 -1.145515 0.602172 0.000000 6 1.223595 0.262789 0.000000 7 -1.290663 -0.693915 0.000000 1 -2.218793 -1.059847 0.000000 1 -0.116879 -1.156914 0.000000 1 -2.011636 1.248340 0.000000 1 0.323428 2.215221 0.000000 1 2.246754 0.611935 0.000000 8 1.061027 -1.025953 0.000000
Keto
/CIS
6 0.064565 1.061283 -0.010828 6 1.297445 0.416338 -0.004881 7 1.344025 -0.930287 0.007487 1 2.293713 -1.260836 0.010892 1 2.196136 1.011775 -0.010897 1 0.074412 2.137855 -0.021087 6 -1.243232 0.472729 -0.006341 8 -1.486854 -0.853710 0.011988 1 -2.122860 1.082640 -0.007781 1 -0.667409 -1.331838 0.012860
TS
6 -0.005934 1.105081 0.000000 6 1.244413 0.438441 0.000000 7 1.161717 -0.851112 0.000000 1 2.000166 -1.393975 0.000000 1 2.176229 0.976465 0.000000 1 -0.041289 2.181105 0.000000 6 -1.256561 0.369448 0.000000 8 -1.240655 -0.879611 0.000000 1 -2.192425 0.908422 0.000000 1 -0.040971 -1.155156 0.000000
Keto
6 -0.025497 1.059485 0.000000 6 1.268847 0.407479 0.000000 7 1.382531 -0.969788 0.000000 1 2.276934 -1.394642 0.000000 1 0.572441 -1.542558 0.000000 1 2.166184 0.988790 0.000000 1 -0.011460 2.136177 0.000000 6 -1.320159 0.454849 0.000000 1 -2.167164 1.138296 0.000000 8 -1.506725 -0.758552 0.000000
3*/B3LYP/Enol
6 0.000000 1.104709 0.000000 6 1.251743 0.504055 0.000000 7 1.302888 -0.877908 0.000000 1 2.266309 -1.219320 0.000000 1 2.150261 1.121926 0.000000 1 -0.059996 2.192145 0.000000 6 -1.274840 0.392412 0.000000 8 -1.340288 -0.949100 0.000000 1 -2.228312 0.909650 0.000000 1 -0.387594 -1.273307 0.000000
TS
6 0.003234 1.126561 0.000000 6 1.254458 0.468285 0.000000 7 1.174241 -0.903728 0.000000 1 2.047380 -1.423109 0.000000 1 2.200430 1.002133 0.000000 1 -0.028806 2.215043 0.000000 6 -1.255235 0.409801 0.000000 8 -1.270364 -0.907068 0.000000 1 -2.206278 0.941945 0.000000 1 -0.084235 -1.181256 0.000000
Keto
/QCISD/Enol
6 .082952 1.095705 .000000 6 1.290391 .429169 .000000 7 1.283527 -.961078 .000000 1 2.240668 -1.319296 .000000 1 2.217786 .998256 .000000 1 .093622 2.182796 .000000 6 -1.253825 .477023 .000000 8 -1.442910 -.866789 .000000 1 -2.159908 1.066797 .000000 1 -.550680 -1.278074 .000000
TS
6 .041120 1.127814 .000000 6 1.271441 .433014 .000000 7 1.135269 -.934220 .000000 1 1.977399 -1.497354 .000000 1 2.235928 .925331 .000000 1 .041004 2.214845 .000000 6 -1.241186 .445876 .000000 8 -1.297431 -.872328 .000000 1 -2.168172 1.013982 .000000 1 -.081838 -1.178869 .000000
Keto
6 -.035282 1.086142 .000000 6 1.284810 .428270 .000000 7 1.343134 -.950647 .000000 1 2.225441 -1.432186 .000000 1 .472246 -1.466870 .000000 1 2.205526 .991736 .000000 1 -.029696 2.174135 .000000 6 -1.307008 .451381 .000000 1 -2.182890 1.113208 .000000 8 -1.468460 -.815030 .000000
3*/CASSCF/Enol
6 0.015732 1.112256 0.000000 6 1.269565 0.562806 0.000000 6 -1.261442 0.404260 0.000000 7 1.428435 -0.823834 0.000000 1 2.404084 -1.068144 0.000000 1 2.132590 1.208053 0.000000 1 -0.059009 2.185941 0.000000 1 -2.195271 0.926997 0.000000 1 -0.504909 -1.336395 0.000000 8 -1.380449 -0.959504 0.000000
TS
6 -0.047859 -1.134678 0.000000 6 1.235692 -0.574300 0.000000 6 -1.254076 -0.327000 0.000000 7 1.262532 0.778674 0.000000 1 2.132050 1.267930 0.000000 1 2.140395 -1.150643 0.000000 1 -0.148090 -2.205997 0.000000 1 -2.214231 -0.819621 0.000000 1 0.196319 1.171842 0.000000 8 -1.188331 0.955176 0.000000
Keto
n/CIS/Enol
6 -0.097582 1.032265 0.000000 6 1.255386 0.501823 0.000000 7 1.595925 -0.779597 0.000000 1 2.401129 -1.365547 0.000000 1 2.105402 1.169508 0.000000 1 -0.148810 2.105532 0.000000 6 -1.269451 0.395656 0.000000 8 -1.497419 -0.943751 0.000000 1 -2.189047 0.948860 0.000000 1 -0.690910 -1.429635 0.000000
TS
6 -0.008921 1.188515 0.000000 6 1.126112 0.394179 0.000000 7 1.095378 -0.881366 0.000000 1 1.733315 -1.642378 0.000000 1 2.118621 0.839823 0.000000 1 -0.015469 2.255960 0.000000 6 -1.140090 0.406070 0.000000 8 -1.144353 -0.854687 0.000000 1 -2.139362 0.839114 0.000000 1 -0.072535 -1.218050 0.000000
Keto
6 0.048511 1.053472 0.000000 6 1.207053 0.384118 0.000000 7 1.403070 -0.978824 0.000000 1 2.321574 -1.347156 0.000000 1 0.645786 -1.617363 0.000000 1 2.114740 0.961470 0.000000 1 0.072317 2.126118 0.000000 6 -1.309623 0.489648 0.000000 1 -2.175398 1.141225 0.000000 8 -1.559518 -0.746993 0.000000
3n3LYP/Enol
6 -0.089980 1.094054 0.000000 6 1.198569 0.534144 0.000000 7 1.502648 -0.789653 0.000000 1 2.284595 -1.426395 0.000000 1 2.090467 1.171040 0.000000 1 -0.153619 2.177658 0.000000 6 -1.279511 0.378547 0.000000 8 -1.373256 -0.990495 0.000000 1 -2.252745 0.857719 0.000000 1 -0.475656 -1.368958 0.000000
TS
6 -0.003282 1.169963 0.000000 6 1.197915 0.449004 0.000000 7 1.169841 -0.918350 0.000000 1 1.863748 -1.652406 0.000000 1 2.184171 0.916312 0.000000 1 -0.005588 2.253661 0.000000 6 -1.203250 0.461293 0.000000 8 -1.222850 -0.906524 0.000000 1 -2.194285 0.907499 0.000000 1 -0.202425 -1.225985 0.000000
Keto
nQCISD/Enol
6 .000000 1.085472 .000000 6 1.256749 .444650 .000000 7 1.464410 -.909062 .000000 1 2.204565 -1.590302 .000000 1 2.186700 1.011893 .000000 1 .018190 2.169206 .000000 6 -1.249111 .481809 .000000 8 -1.487245 -.876231 .000000 1 -2.167927 1.053082 .000000 1 -.640263 -1.342181 .000000
TS
6 -.001576 1.175513 .000000 6 1.204847 .459759 .000000 7 1.138484 -.917846 .000000 1 1.819832 -1.659507 .000000 1 2.194572 .904323 .000000 1 -.012197 2.257292 .000000 6 -1.199206 .461302 .000000 8 -1.206225 -.915904 .000000 1 -2.193809 .889985 .000000 1 -.152373 -1.219385 .000000
Keto
6 .003898 1.085935 .000000 6 1.225234 .406006 .000000 7 1.367834 -.974781 .000000 1 2.280417 -1.390900 .000000 1 .570644 -1.587578 .000000 1 2.151465 .967129 .000000 1 .036404 2.169357 .000000 6 -1.278932 .521091 .000000 1 -2.197244 1.104195 .000000 8 -1.514716 -.814616 .000000
3nCASSCF/Enol
6 -0.062168 1.075029 0.000000 6 1.246800 0.566220 0.000000 6 -1.263781 0.392544 0.000000 7 1.590146 -0.761544 0.000000 1 2.395495 -1.340750 0.000000 1 2.098929 1.222421 0.000000 1 -0.136903 2.147258 0.000000 1 -2.199599 0.915154 0.000000 1 -0.604220 -1.409474 0.000000 8 1 -.11748 2.03151 .00000
TS
6 0.189435 1.172599 0.000000 6 -1.120252 0.683358 0.000000 6 1.230633 0.258143 0.000000 7 -1.267385 -0.687020 0.000000 1 -2.055848 -1.291764 0.000000 1 -0.125272 -1.195586 0.000000 1 -2.009641 1.284091 0.000000 1 0.392798 2.225540 0.000000 1 2.276658 0.496432 0.000000 8 0.980486 -1.080305 0.000000
Keto
Adiabatic excitation energies from S
oto the
and
n
excited states (in kcal mol
).
S
o
S
on
Enol
Keto
Enol
Keto
HF(CIS)
59.3
67.8
104.6
100.1
MP2//HF(CIS-MP2//CIS)
110.3
110.5
141.0
125.4
B3LYP
61.0
63.1
86.7
73.8
QCISD
63.8
64.0
90.9
76.2
CCSD(T)//QCISD
69.6
66.1
94.2
78.4
CASSCF
83.0
91.6
129.4
106.7
CASSCF//HF(CIS)
86.3
86.6
132.0
112.0
CASSCF//QCISD
67.5
73.2
108.1
94.2
CASPT2//HF(CIS)
77.5
73.6
108.2
83.7
CASPT2//QCISD
61.1
65.8
86.5
75.5
Keto-enol relative energies and proton transfer energy barriers (in kcal mol
), both referred to the enol structure, for the ground state and the
and
n
*excited states.
S
o
* n
*
E
k-e
E
‡ts-e
E
k-e
E
‡ts-e
E
k-e
E
‡ts-eHF(CIS)
-8.7
8.7
-0.1
26.1
-13.1
34.3
MP2//HF(CIS-MP2//CIS)
-7.1
0.6
-6.9
4.2
-22.7
4.1
B3LYP
a-6.9 (-7.3)
0.9 (1.1)
-4.8 (-5.1)
3.4 (3.6)
-19.8 (-19.7)
2.4 (2.9)
B3LYP//(HF-CIS)
-7.9
-0.9
-4.8
6.8
-17.9
12.0
B3LYP//CASSCF
-8.2
-1.5
-5.4
0.3
-20.4
0.9
B3LYP//QCISD
-7.3
0.3
-4.9
2.8
-19.8
2.1
QCISD
-6.0
4.5
-2.1
9.5
-21.2
7.8
CCSD(T)//QCISD
-5.2
3.9
-1.7
8.2
-21.0
5.8
CASSCF
-11.1
11.1
2.3
36.8
-25.0
29.4
CASSCF//HF(CIS)
-12.3
c9.3
c-5.5
33.4
-19.5
42.5
CASSCF//B3LYP
-14.1
6.2
-6.6
18.8
-26.0
20.6
CASSCF//QCISD
-11.7
9.8
-6.0
21.6
-25.6
26.3
CASPT2//HF(CIS)
-3.6
c3.9
c2.4
7.0
-19.5
7.8
CASPT2//B3LYP
-1.9
6.7
0.9
5.3
-19.3
6.0
CASPT2//QCISD
-3.5
5.2
1.2
6.9
-19.1
4.1
CASPT2//CASSCF
-4.0
3.2
-0.8
4.5
-19.0
1.1