Computer Modeling and Simulations on Flexible Bifunctional
Systems: Intramolecular Energy Transfer Implications

J 2003

Computer Modeling and Simulations on Flexible Bifunctional Systems: Intramolecular Energy Transfer Implications

VRBKA, Luboš, Petr KLÁN, Zdeněk KŘÍŽ, Jaroslav KOČA, Peter J. WAGNER et. al.

Základní údaje

Originální název

Computer Modeling and Simulations on Flexible Bifunctional Systems: Intramolecular Energy Transfer Implications

Autoři

VRBKA, Luboš (203 Česká republika), Petr KLÁN (203 Česká republika, garant), Zdeněk KŘÍŽ (203 Česká republika), Jaroslav KOČA (203 Česká republika) a Peter J. WAGNER (840 Spojené státy)

Vydání

Journal of Physical Chemistry A, USA, The American Chemical Society, 2003, 1089-5639

Další údaje

Jazyk

angličtina

Typ výsledku

Článek v odborném periodiku

Obor

10401 Organic chemistry

Stát vydavatele

Spojené státy

Utajení

není předmětem státního či obchodního tajemství

Impakt faktor

Impact factor: 2.792

Kód RIV

RIV/00216224:14310/03:00008683

Organizační jednotka

Přírodovědecká fakulta

UT WoS

000182732800032

Klíčová slova anglicky

computational; simulation; flexibility; energy transfer

Štítky

computational, energy transfer, Flexibility, simulation

Příznaky

Mezinárodní význam

Změněno: 9. 2. 2007 14:21, prof. RNDr. Petr Klán, Ph.D.

Anotace

V originále

The conformational search of the potential energy surface using the single coordinate driving method CICADA, molecular dynamics calculations, and quantum mechanical studies using the 6-31G* basis set were used for a detailed analysis of the conformational behavior of various flexible bichromophoric compounds Ph-CO-(CH2)x-O-Ar (x = 3-14; Ar = 2-naphthyl, 2-biphenylyl, 3-biphenylyl, 4-biphenylyl). The results were used for the estimation of the end-to-end intramolecular (exchange) energy transfer efficiency and for comparison to the data recently obtained from the steady-state quenching and quantum yield measurements (Wagner, P. J.; Klan, P. J. Am. Chem. Soc. 1999, 121, 9626-9635). The conformational search clearly supported the dominance of the through-space interaction in longer molecules (x = 5-14), which was still remarkably high even for x = 14. Comparing both computational and experimental results, a ~90% through-bond coupling was estimated for the shortest (x = 3) bichromophores. The molecular dynamics calculations seemed to validate the fact that only a small fraction of ground-state conformations involved ground-state control (static quenching) with the interchromophore distances within 4 Ĺ. Rate-determining bond rotations to such geometries should be then responsible for the energy transfer within the lifetime of the excited donor. The influence of chromophore orientation was found insignificant for long-tether molecules, but important in short-tether ones due to different reactive volumes of different acceptors, such as naphthalene or biphenyl. In addition, a correlation of the calculated average distances between the gamma-hydrogen and the carbonyl oxygen with the experimental hydrogen abstraction rate constants in the Norrish type II process strongly supported the right choice of the computational method.

Návaznosti

MSM 143100005, záměr

Název: Strukturně-funkční vztahy biomolekul a jejich role v metabolismu

Investor: Ministerstvo školství, mládeže a tělovýchovy ČR, Strukturně-funkční vztahy biomolekul a jejich role v metabolismu

Citovat

VRBKA, Luboš, Petr KLÁN, Zdeněk KŘÍŽ, Jaroslav KOČA a Peter J. WAGNER. Computer Modeling and Simulations on Flexible Bifunctional Systems: Intramolecular Energy Transfer Implications. Journal of Physical Chemistry A. USA: The American Chemical Society, 2003, roč. 107, č. 18, s. 3404-3414. ISSN 1089-5639.

@article{486318,
   author = {Vrbka, Luboš and Klán, Petr and Kříž, Zdeněk and Koča, Jaroslav and Wagner, Peter J.},
   article_location = {USA},
   article_number = {18},
   keywords = {computational; simulation; flexibility; energy transfer},
   language = {eng},
   issn = {1089-5639},
   journal = {Journal of Physical Chemistry A},
   title = {Computer Modeling and Simulations on Flexible Bifunctional Systems: Intramolecular Energy Transfer Implications},
   volume = {107},
   year = {2003}
}

TY  - JOUR
ID  - 486318
AU  - Vrbka, Luboš - Klán, Petr - Kříž, Zdeněk - Koča, Jaroslav - Wagner, Peter J.
PY  - 2003
TI  - Computer Modeling and Simulations on Flexible Bifunctional Systems: Intramolecular Energy Transfer Implications
JF  - Journal of Physical Chemistry A
VL  - 107
IS  - 18
SP  - 3404
EP  - 3404
PB  - The American Chemical Society
SN  - 10895639
KW  - computational
KW  - simulation
KW  - flexibility
KW  - energy transfer
N2  - The conformational search of the potential energy surface using the single coordinate driving method CICADA, molecular dynamics calculations, and quantum mechanical studies using the 6-31G* basis set were used for a detailed analysis of the conformational behavior of various flexible bichromophoric compounds Ph-CO-(CH2)x-O-Ar (x = 3-14; Ar = 2-naphthyl, 2-biphenylyl, 3-biphenylyl, 4-biphenylyl). The results were used for the estimation of the end-to-end intramolecular (exchange) energy transfer efficiency and for comparison to the data recently obtained from the steady-state quenching and quantum yield measurements (Wagner, P. J.; Klan, P. J. Am. Chem. Soc. 1999, 121, 9626-9635). The conformational search clearly supported the dominance of the through-space interaction in longer molecules (x = 5-14), which was still remarkably high even for x = 14. Comparing both computational and experimental results, a ~90% through-bond coupling was estimated for the shortest (x = 3) bichromophores. The molecular dynamics calculations seemed to validate the fact that only a small fraction of ground-state conformations involved ground-state control (static quenching) with the interchromophore distances within 4 Ĺ. Rate-determining bond rotations to such geometries should be then responsible for the energy transfer within the lifetime of the excited donor. The influence of chromophore orientation was found insignificant for long-tether molecules, but important in short-tether ones due to different reactive volumes of different acceptors, such as naphthalene or biphenyl. In addition, a correlation of the calculated average distances between the gamma-hydrogen and the carbonyl oxygen with the experimental hydrogen abstraction rate constants in the Norrish type II process strongly supported the right choice of the computational method.
ER  -

VRBKA, Luboš, Petr KLÁN, Zdeněk KŘÍŽ, Jaroslav KOČA a Peter J. WAGNER. Computer Modeling and Simulations on Flexible Bifunctional Systems: Intramolecular Energy Transfer Implications. \textit{Journal of Physical Chemistry A}. USA: The American Chemical Society, 2003, roč.~107, č.~18, s.~3404-3414. ISSN~1089-5639.

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