11 February 2000

Chemical Physics Letters 317 Ž2000. 545–552

www.elsevier.nlrlocatercplett

Comparison of the electronic excitation spectra of chlorophyll a

and pheophytin a calculated at density functional theory level
)
Dage Sundholm
Department of Chemistry, P.O. Box 55 (A.I. Virtasen aukio 1) FIN-00014 Helsinki, Finland
Received 24 June 1999; in final form 13 December 1999

Abstract

The molecular structures of chlorophyll a and pheophytin a, with the phytyl group replaced by a hydrogen, have been
optimized at the density functional theory ŽDFT. level. The excitation energies and oscillator strengths obtained at the DFT
level using the time-dependent perturbation theory approach are compared to experimental data. In the visible region, 12
electronic transitions are obtained which is in a good agreement with the experimental observations. The present calculations
show that Gouterman’s generally accepted four-orbital model does not correctly describe the excitation spectrum of
chlorophylls. q 2000 Elsevier Science B.V. All rights reserved.

1. Introduction called Q x , Q y , B x and B y of which the Q bands are

weak and found at about 500–700 nm, while the
The visible part of the electronic absorption spec-
intense B bands appear at 350–450 nm. For
tra of porphyrins and chlorophylls plays a central
metallo-porphyrins which may have a local D4h sym-
role in many biological systems and has therefore
metry the two Q bands as well as the the two B
been the subject of many experimental and theoreti-
bands are degenerate. The porphyrin nucleus of met-
cal studies w1–10x. The interpretation of the elec-
allo-chlorins such as chlorophyll a and pheophytin a
tronic excitation spectra of porphyrins and metallo-
has locally a lower symmetry than D4h and therefore
porphyrins relies mainly on the four-orbital model
four excitation bands would be expected. Since the
originally suggested by Gouterman w1,2,8x. In
experimental chlorophyll spectra possess more than
Gouterman’s theory, only the two highest occupied
four absorption maxima, a more sophisticated model
molecular orbitals ŽHOMO. and two lowest unoccu-
which considers the metal-ion and ring-vibrational
pied molecular orbitals ŽLUMO. are considered. In
effects is needed for their interpretation w11x.
this four-orbital space, four singly excited configura-
Computationally, the electronic spectra of chloro-
tions can be constructed. The electronic excitations
phylls have been studied at semi-empirical w1,3,
from the ground state to the four configurations Žor
12,13x, density functional theory ŽDFT. w10x, and ab
actually to the linear combinations of the configura-
initio w9x levels of theory. The most extensive calcu-
tions. result in four bands. These bands are usually
lations on chlorophylls are the time-dependent DFT
ŽTD-DFT. calculations on chlorophyll a including
)
Fax: q358-9-191-40169; e-mail: sundholm@chem.helsinki.fi the phytyl chain w10x and the symmetry-adapted clus-

0009-2614r00r$ - see front matter q 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 0 0 9 - 2 6 1 4 Ž 9 9 . 0 1 4 2 8 - 1
546 D. Sundholmr Chemical Physics Letters 317 (2000) 545–552
ter configuration interaction ŽSAC-CI. calculations
by Hasegawa et al. w9x on chlorophyll a and pheo-
phytin a with the phytyl group and some other
substituents replaced by hydrogens. In this work, the
molecular structures of chlorophyll a and pheophytin
a have been optimized at the DFT level. The near-ul-
traviolet ŽUV. and the visible part of the electronic
absorption spectra have been calculated using the
TD-DFT approach. Similar calculations on free-base
porphin w14x, magnesium porphyrin, and magnesium
etioporphyrin I w15x will be published separately.
Since the phytyl chain is not expected to signifi-
cantly affect the absorption spectra, the phytyl group
has been replaced by a hydrogen. This assumption is
checked by comparing the obtained excitation spec-
trum for chlorophyll a, with a hydrogen instead of
the phytyl chain, with the excitation spectrum of the
full chlorophyll a molecule w10x. The differences in
the calculated excitation energies and oscillator
strengths for chlorophyll a and pheophytin a pro-
vide information about the effect of magnesium on
the absorption spectra of chlorophylls.
2. Computational methods
The molecular structures of chlorophyll a and
pheophytin a have been optimized at the DFT level
w16x using the Becke–Perdew ŽBP. parametrization
w17–19x as implemented in TURBOMOLE w20x. The
excitation energies have been calculated at the DFT
level using the time-dependent perturbation theory
approach ŽTD-DFT. w21–23x which is based on the
Runge–Gross theorem w24x and related to the linear
response Hartree–Fock ŽLR-HF. or random-phase
approximation ŽRPA. method w25x. In the present
implementation of the DFT method w16,21,22x, the
resolution of the identity ŽRI. approach is used for
the treatment of Coulomb-type matrix elements and
thereby one achieves a significant reduction in the
computational costs.
3. Basis sets
In this study, split-valence basis sets augmented
with polarization functions on the C, N, O, and Mg
atoms ŽSVŽP.. have been employed. The sp parts
Žs part for hydrogen. of the basis sets are optimized
for atoms at the self-consistent-field ŽSCF. level
w26,27x while the exponents of the polarization func-
tions are 0.8, 1.0, 1.2 and 0.189 for C, N, O, and
Mg, respectively w28x. The optimized auxiliary basis
sets used in the RI-DFT calculations consist of
4s2pr2s1p for H, of 12s4p4d1fr5s2p2d1f for Mg,
and of 8s3p3d1fr6s3p3d1f for C, N, and O.
4. Results
4.1. Molecular structures
The molecular structures of chlorophyll a and
pheophytin a have been obtained as described in the
previous sections. The Cartesian coordinates of
chlorophyll a and pheophytin a with the phytyl
group replaced by a hydrogen are available on our
internet page w29x. The molecular structures are
shown in Figs. 1 and 2.
For chlorophylls, the rings are often numbered
clockwise starting from the pyrrole ring with the
C 2 H 3 substituent and ending at the pyrroline ring to
which the phytyl chain is attached. The cyclopen-
tanone ring is the fifth ring. The accuracy of the
bond lengths for the DFT structures is estimated to
be about 1 pm w10x. By comparing the bond distances
and the bond angles of the chlorophyll a without the
phytyl chain w29x with the corresponding bond dis-
Fig. 1. Molecular structure of chlorophyll a with a hydrogen
instead of the phytyl chain. The Cartesian coordinates Žin a.u.. can
be downloaded from our internet page w29x.
 D. Sundholmr Chemical Physics Letters 317 (2000) 545–552 547

group. The phytyl group was replaced by a hydrogen

Fig. 2. Molecular structure of pheophytin a with a hydrogen
instead of the phytyl chain. The Cartesian coordinates Žin a.u.. can
be downloaded from our internet page w29x.
tances and angles of the full chlorophyll a
moleculew30x, it is seen that the chlorophyll a struc-
ture is hardly affected by the presence of the phytyl
also for pheophytin a.
For pheophytin a, the inner hydrogens are as-
sumed to be connected to the nitrogens of rings 1
and 3. This assumption will not significantly affect
the results of this work. The transition barriers for
the inner proton migration are about 10–15 kcal
moly1 w31x which means that the inner hydrogens
will not have any fixed positions but all isomers are
present at room temperature.
The N–N distances for the two chlorophylls are
practically identical. For pheophytin a, the distance
between the nitrogens with the two inner hydrogens
is 6 pm longer than the corresponding distance for
chlorophyll a, reflecting the size of the inner hydro-
gens. The N–N distance between the nitrogens with-
out any hydrogens across the porphyrin nucleus is
practically the same for the two chlorophylls as for
pheophytin a.
The remarkably long C–C distance in the cy-
clopentanone ring of chlorophyll a w10x is also ob-
tained in chlorophyll a without the phytyl group. For

Table 1
Comparison of the calculated excitation energies Ž E in eV and l in nm. and the oscillator strengths Ž f . for chlorophyll a without the phytyl
group with the experimental dataa for the full chlorophyll a molecule
State EŽCalc. lŽCalc. f ŽCalc. lŽExp. f ŽExp. b Ref.
1 y1 y1 Ž
2 A 2.00 620 1.86 = 10 663, 670 2.3 = 10 s. w2,3,7,8x
3 1A 2.04 607 2.67 = 10y2 618, 649 m w2,7,8x
4 1A 2.16 573 1.03 = 10y2 580, 635 m w2,7,8x
5 1A 2.32 533 3.86 = 10y3 535, 557 w w2,7,8x
6 1A 2.51 493 5.78 = 10y3
7 1A 2.76 450 1.62 = 10y1 431, 436 1.1c Žs. w2,3,7,8x
8 1A 2.80 443 1.15 = 10y1
9 1A 2.83 438 1.86 = 10y1
10 1A 2.94 421 2.40 = 10y2
11 1A 2.97 417 1.85 = 10y1 409, 429 s w2,7x
12 1A 3.01 412 6.28 = 10y3
13 1A 3.08 402 4.01 = 10y2
14 1A 3.20 387 2.84 = 10y2
15 1A 3.29 376 2.72 = 10y1 380, 389 m w2,7x
16 1A 3.43 362 3.26 = 10y1 377 m w7x
17 1A 3.45 360 1.25 = 10y1
18 1A 3.48 356 7.12 = 10y2
19 1A 3.58 346 3.34 = 10y2 346 m w7x
20 1A 3.60 344 7.37 = 10y2
21 1A 3.64 340 4.54 = 10y3
a
The reported experimental wavelengths differ due to environmental effects and due to the interpretation of the spectrum.
b
s s strong, m s medium, w s weak.
c
The oscillator strength includes all transitions in this wavelength region.
548 D. Sundholmr Chemical Physics Letters 317 (2000) 545–552

Table 2 4.2. Chlorophyll spectrum

Comparison of the transition wavelengths Žin nm. and the corre-
sponding oscillator strengths for chlorophyll a with w10x and
without the phytyl group The visible part of the excitation spectrum for
Without phytyl With phytyl chlorophyll a without the phytyl group is very simi-
lar to the calculated spectrum of the full chlorophyll
State l f State l f
1 y1 1
a molecule and to the experimental spectrum. In the
2 A 620 1.86=10 2 A 621 1.82=10y1
Q band region Žbetween 500 and 700 nm. four
3 1A 607 2.67=10y2 3 1A 609 2.60=10y2
4 1A 573 1.0=10y3 4 1A 570 1.0=10y3 excited states are obtained which agrees well with
5 1A 533 3.9=10y3 5 1A 533 3.7=10y3 the interpretation of the experimental spectrum by
6 1A 494 5.8=10y3 6 1A 493 6.0=10y3 Fragata et al. w7x. They obtained the four lowest
7 1A 490 6.1=10y4 transitions at 670, 649, 635 and 557 nm which can
7 1A 450 1.62=10y1 8 1A 451 1.82=10y1
be compared to the present calculated values of 620,
8 1A 443 1.15=10y1 9 1A 445 6.50=10y2
10 1A 442 5.71=10y2 607, 573 and 533 nm. Experimentally, the transitions
9 1A 438 1.86=10y1 11 1A 435 1.84=10y1 at 436 nm was assign to the B band. In the TD-DFT
10 1A 421 2.40=10y2 calculations, the B band consists of three strong
11 1A 418 1.85=10y1 12 1A 417 1.60=10y1 transitions at 450, 443 and 438 nm. The subsequent
12 1A 412 6.3=10y3 13 1A 412 1.00=10y2
experimental transitions are observed at 429, 389,
13 1A 402 4.01=10y2 14 1A 404 3.91=10y2
14 1A 387 2.84=10y2 15 1A 389 1.0=10y4 377 and 346 nm. In this energy range, the computa-
tional spectrum contains about 10 excited states. Of
these, the strongest transitions appear at 417, 376,
pheophytin a, this C–C distance is found to be about 362 and 360 nm which again are in an excellent
1 pm shorter than for chlorophyll a or 158.5 pm. agreement with the observed spectrum. In Table 1,

Table 3
The comparison of the calculated transition wavelengths Ž l in nm., the excitation energies Ž E in eV., and the oscillator strengths Ž f . for
pheophytin a with the corresponding experimental data
State lŽCalc. EŽCalc. f ŽCalc. lŽExp. a f ŽExp. b Ref.
1 y1
2 A 622 1.99 1.28 = 10 672,667 s w7,2x
3 1A 604 2.05 2.83 = 10y2 670,609 s w7,2x
665,561 w w7,2x
4 1A 554 2.24 5.= 10y5 540,533 m w7,2x
5 1A 538 2.31 4.1 = 10y3 510,506 m w7,2x
6 1A 477 2.60 1.39 = 10y2 484,470 w w7,2x
7 1A 454 2.73 2.62 = 10y1 416,408 vs w7,2x
8 1A 442 2.80 2.93 = 10y2
9 1A 439 2.82 4.90 = 10y2
10 1A 435 2.85 2.21 = 10y1 395 s w7x
11 1A 416 2.98 1.88 = 10y2
12 1A 411 3.02 3.99 = 10y2
13 1A 402 3.08 7.59 = 10y2
14 1A 393 3.16 2.1 = 10y3
15 1A 391 3.17 9.12 = 10y2
16 1A 382 3.24 8.65 = 10y2
17 1A 377 3.29 3.90 = 10y1 334 s w7x
18 1A 367 3.38 3.98 = 10y1
19 1A 363 3.42 1.73 = 10y2
20 1A 352 3.52 2.40 = 10y2
21 1A 347 3.56 2.88 = 10y2

a
The position of the Ž0,0. bands of Ref. w7x. The Q y Ž0,0., Q y Ž1,0., Q y Ž2,0., Q x Ž0,0., Q x Ž1,0., Q x Ž2,0., and the B band, respectively, as
interpreted in Ref. w2x.
b
vs s very strong, s s strong, m s medium, w s weak.
 D. Sundholmr Chemical Physics Letters 317 (2000) 545–552 549

the calculated excitation energies for chlorophyll a Hasegawa et al. w9x calculated the excitation spec-
without the phytyl group are compared to experimen- tra for pheophytin a at the SAC-CI level. They
tal data. obtained only two transitions in the Q band and two
At the SAC-CI level w9x, the excitation spectra for in the B band, which is in agreement with Gouter-
chlorophyll a is much simpler. Only four excited man’s four-orbital model and with the interpretation
states are obtained in the visible and near-UV region, of Houssier and Sauer w2x. However, their results are
while experimentally about nine excited states have neither in agreement with the present TD-DFT re-
been identified in the same energy range w7x. sults nor with the experimental interpretation by
The excitation spectrum for chlorophyll a is not Fragata et al. w7x.
much affected by the phytyl group. The sixth excited
state which is a very weak transition at 490 nm is 4.4. Comparison of the pheophytin and chlorophyll
apparently due to the presence of the phytyl group. spectra
For the full chlorophyll a molecule, the tenth excited
state is obtained at 442 nm, while for chlorophyll a A comparison of the experimental spectra for
without the phytyl group, the same state appears at chlorophyll a and pheophytin a Žsee, e.g., Ref. w7x.
421 nm. The tenth transition and the strong transition shows that for chlorophyll a the first Q transition is
of the B band appear in the opposite order for the more intense than for pheophytin a. At the TD-DFT
two chlorophyll molecules. As seen in Table 2, the level, the oscillator strength for the first transition of
oscillator strengths are also almost unaffected by the chlorophyll a is about 50% larger than for pheo-
phytyl group. phytin a. Another apparent difference in the Q band
of the two experimental spectra are the two humps in
4.3. Pheophytin spectrum the 500 nm region of the pheophytin a spectrum
which are not as intense in the chlorophyll a spec-
In Table 3, the calculated excitation energies and
oscillator strengths of pheophytin a without the
Table 4
phytyl group are compared to experimental data. For The comparison of the calculated transition wavelengths and the
pheophytin a, there is also a one-to-one correspon- corresponding oscillator strengths for chlorophyll a and pheo-
dence between the calculated excitation energies and phytin a Žin nm.. The phytyl group is replaced by a hydrogen
the experimental absorption maxima. State Chlorophyll Pheophytin
Houssier and Sauer w2x assumed that the spectra of l f l f
chlorophylls can be assigned on the basis of Gouter- 2 1A 620 1.86=10y1 622 1.28=10y1
man’s four-orbital model and interpreted the second 3 1A 607 2.67=10y2 604 2.83=10y2
and third transitions as vibrational overtones of the 4 1A 573 1.0=10y3 554 5.=10y5
electronic Q y transition and the fifth and sixth transi- 5 1A 533 3.9=10y3 538 4.1=10y3
tions as vibrational overtones of the electronic Q x 6 1A 494 5.8=10y3 477 1.39=10y2
7 1A 450 1.62=10y1 454 2.62=10y1
transition. On the other hand, Fragata et al. w7x 8 1A 443 1.15=10y1 442 2.93=10y2
suggested that all six Q transitions are true elec- 9 1A 438 1.86=10y1 439 4.90=10y2
tronic transitions. Since, at the TD-DFT level, six 10 1A 421 2.40=10y2 435 2.21=10y1
electronic transitions are obtained in the Q band 11 1A 418 1.85=10y1 416 1.88=10y2
region, the interpretation by Fragata et al. w7x is 12 1A 412 6.3=10y3 411 3.99=10y2
13 1A 402 4.01=10y2 402 7.59=10y2
probably more correct than the traditional interpreta- 14 1A 387 2.84=10y2 393 2.1=10y3
tion based on Gouterman’s four-orbital model. How- 15 1A 377 2.72=10y1 391 9.12=10y2
ever, their suggestion that there are three almost 16 1A 362 3.26=10y1 382 8.65=10y2
degenerate transitions at about 670 nm is not sup- 17 1A 360 1.25=10y1 377 3.90=10y1
ported by the present TD-DFT calculations. The 18 1A 356 7.12=10y2 367 3.98=10y1
19 1A 346 3.34=10y2 363 1.73=10y2
present TD-DFT calculations suggest that each tran- 20 1A 344 7.37=10y2 352 2.40=10y2
sition maximum corresponds to an electronic transi- 21 1A 340 4.5=10y3 348 2.88=10y2
tion.
550 D. Sundholmr Chemical Physics Letters 317 (2000) 545–552

trum. The intense peak between 320 and 450 nm of
the chlorophyll a spectrum has four distinct absorp-
tion maxima, while for pheophytin a this peak con-
sists of only two maxima. However, a careful study
of the spectrum reveals several small peaks in the
pheophytin a spectrum between 340 and 400 nm.
The comparison of the TD-DFT spectra for
chlorophyll a and pheophytin a does not show any
large differences. Approximately the same transition
energies were obtained for both molecules. The
wavelengths of electronic excitations in the Q band
region differ by less than 20 nm. The oscillator
strengths are also very similar. The two humps at
about 500 nm in the experimental spectrum for
pheophytin a seem to be due to somewhat different
oscillator strengths. The largest relative difference in
the oscillator strength for chlorophyll a and pheo-
phytin a appears for the sixth transition. For this
transition, the oscillator strength for pheophytin a is
2.5 times larger than for chlorophyll a. This could
explain the presence of the fourth peak in the experi-
mental spectrum for pheophytin a. For chlorophyll
a, a few tiny maxima can be seen in the experimental
spectrum at 500–550 nm. These peaks might corre-
spond to the two peaks at about the same wave-
lengths in the pheophytin a spectrum. The calculated
excitation spectra for chlorophyll a and pheophytin
a are compared in Table 4. The interpretation of the
Q band is further complicated by the presence of the
vibrational effects.
As seen in Table 4, the strong band at about 400
nm consists for chlorophyll a of three strong transi-
tions at 450, 443 and 438 nm, while pheophytin a
has in this energy range one dominating transition at
435 nm. The transition at 435 nm is approximately
one order of magnitude stronger than the other tran-
sitions in this region of the spectrum. For chlorophyll
a additional strong transitions are obtained at 418,
377, 362 and 360 nm which cause the additional
maxima on the high-energy side of the B band. For

Table 5
The most important excitation weights Žin%. for the excited states and the corresponding excitation energies Ž E in eV. of chlorophyll a and
pheophytin a
Chlorophyll Pheophytin
State Excit.a Weight E Excit.b Weight E
™ 163a ™ 158a
™ 164 a ™ 159a
1
2 A 162 a 82 2.00 157a 74 1.99

™ 163a ™ 158a
161a 18 156 a 25

™ 164 a ™ 159a
3 1A 161a 73 2.04 156 a 77 2.05

™ 163a ™ 158a
162 a 20 157a 19

™ 158a
4 1A 160 a 94 2.16 154 a 54 2.24

159a ™ 163a ™ 158a

155a 45

™ 158a
1
5 A 92 2.32 155a 54 2.31

158a ™ 163a ™ 158a

154 a 43

160 a ™ 164 a ™ 159a

6 1A 98 2.51 153a 89 2.60

161a ™ 164 a ™ 159a

7 1A 39 2.76 156 a 46 2.73

162 a ™ 164 a ™ 160 a

22 154 a 15

161a ™ 165a ™ 158a

18 156 a 14

160 a ™ 164 a ™ 159a

8 157a 12

162 a ™ 164 a ™ 159a

8 1A 44 2.80 154 a 44 2.80

157a ™ 163a ™ 158 a

28 155a 35

161a ™ 163a
9 152 a 11

161a ™ 164 a 152 a ™ 158 a

6

157a ™ 163a 154 a ™ 159a

9 1A 28 2.83 69 2.82

160 a ™ 164 a 157a ™ 159a

18 8

156 a ™ 163a 155a ™ 159a

15 8

161a ™ 165a
15 7

162 a ™ 163a
6
6
a
For chlorophyll a orbitals 162a and 163a are HOMO and LUMO, respectively.
b
For pheophytin a orbitals 157a and 158a are HOMO and LUMO, respectively.
 D. Sundholmr Chemical Physics Letters 317 (2000) 545–552 551

pheophytin a, only two strong transitions are ob- are very similar. The main reason for their different
tained in the same energy range or at 377 and 367 absorption spectra seems to originate from differ-
nm, which probably result in the absorption maxi- ences in the oscillator strengths rather than differ-
mum observed at 334 nm. ences in transition energies.
The excitation weights for the eight lowest ex-
cited states of chlorophyll a and pheophytin a are
given in Table 5. The excitation weights for the two Acknowledgements
molecules are similar. The main differences appear
for the 4 1A, 5 1A, and 9 1A states. For chlorophyll a, I would like to thank Professor R. Ahlrichs for a
the 4 1A and 5 1A states are dominated by one single recent version of TURBOMOLE and Dr. H. Konschin
excitation, while for pheophytin a these states are for discussions.
mixed. As seen in Table 5, the two first transitions
can be assigned to the two Gouterman Q transitions,
while the 7 1A–13 1A states have excitation coeffi-
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