SUPP257.DOC 71KB Jun 05 2011 09:30:51 PM

(1)

(2)

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/Enol

6 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

(3)

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

(4)

/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

(5)

/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

(6)

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

3_n_{3LYP/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

(7)

nQCISD/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

3_n_{CASSCF/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

(8)

Adiabatic excitation energies from S

o

to the



and

n



excited states (in kcal mol

).

S

o





S

_o

n





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

(9)

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-e

HF(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

c

9.3

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

c

3.9

c

2.4

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