Local electric fields and molecular properties in heterogeneous environments through polarizable embedding

被引:58
作者
List, Nanna Holmgaard [1 ]
Jensen, Hans Jorgen Aagaard [1 ]
Kongsted, Jacob [1 ]
机构
[1] Univ Southern Denmark, Campusvej 55, DK-5230 Odense M, Denmark
关键词
DENSITY-FUNCTIONAL-THEORY; NONLINEAR-OPTICAL PROPERTIES; CIRCULAR-DICHROISM SPECTRA; ABSORPTION CROSS-SECTIONS; DIPOLE INTERACTION-MODEL; CONTINUUM MODEL; FLUORESCENT PROTEINS; 2-PHOTON ABSORPTION; BASIS-SETS; CHARGE-TRANSFER;
D O I
10.1039/c6cp00669h
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
In spectroscopies, the local field experienced by a molecule embedded in an environment will be different from the externally applied electromagnetic field, and this difference may significantly alter the response and transition properties of the molecule. The polarizable embedding (PE) model has previously been developed to model the local field contribution stemming from the direct molecule-environment coupling of the electromagnetic response properties of molecules in solution as well as in heterogeneous environments, such as proteins. Here we present an extension of this approach to address the additional effective external field effect, i.e., the manifestations of the environment polarization induced by the external field, which allows for the calculation of properties defined in terms of the external field. Within a response framework, we report calculations of the one-and two-photon absorption (1PA and 2PA, respectively) properties of PRODAN-methanol clusters as well as the fluorescent protein DsRed. Our results demonstrate the necessity of accounting for both the dynamical reaction field and effective external field contributions to the local field in order to reproduce full quantum chemical reference calculations. For the lowest pi -> pi* transition in DsRed, inclusion of effective external field effects gives rise to a 1.9-and 3.5-fold reduction in the 1PA and 2PA cross-sections, respectively. The effective external field is, however, strongly influenced by the heterogeneity of the protein matrix, and the resulting effect can lead to either screening or enhancement depending on the nature of the transition under consideration.
引用
收藏
页码:10070 / 10080
页数:11
相关论文
共 85 条
[1]   The Dalton quantum chemistry program system [J].
Aidas, Kestutis ;
Angeli, Celestino ;
Bak, Keld L. ;
Bakken, Vebjorn ;
Bast, Radovan ;
Boman, Linus ;
Christiansen, Ove ;
Cimiraglia, Renzo ;
Coriani, Sonia ;
Dahle, Pal ;
Dalskov, Erik K. ;
Ekstrom, Ulf ;
Enevoldsen, Thomas ;
Eriksen, Janus J. ;
Ettenhuber, Patrick ;
Fernandez, Berta ;
Ferrighi, Lara ;
Fliegl, Heike ;
Frediani, Luca ;
Hald, Kasper ;
Halkier, Asger ;
Hattig, Christof ;
Heiberg, Hanne ;
Helgaker, Trygve ;
Hennum, Alf Christian ;
Hettema, Hinne ;
Hjertenaes, Eirik ;
Host, Stinne ;
Hoyvik, Ida-Marie ;
Iozzi, Maria Francesca ;
Jansik, Branislav ;
Jensen, Hans Jorgen Aa. ;
Jonsson, Dan ;
Jorgensen, Poul ;
Kauczor, Joanna ;
Kirpekar, Sheela ;
Kjrgaard, Thomas ;
Klopper, Wim ;
Knecht, Stefan ;
Kobayashi, Rika ;
Koch, Henrik ;
Kongsted, Jacob ;
Krapp, Andreas ;
Kristensen, Kasper ;
Ligabue, Andrea ;
Lutnaes, Ola B. ;
Melo, Juan I. ;
Mikkelsen, Kurt V. ;
Myhre, Rolf H. ;
Neiss, Christian .
WILEY INTERDISCIPLINARY REVIEWS-COMPUTATIONAL MOLECULAR SCIENCE, 2014, 4 (03) :269-284
[2]   RAYLEIGH-SCHRODINGER PERTURBATION-THEORY FOR NONLINEAR SCHRODINGER-EQUATIONS WITH LINEAR PERTURBATION [J].
ANGYAN, JG .
INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, 1993, 47 (06) :469-483
[3]   COMMON THEORETICAL FRAMEWORK FOR QUANTUM CHEMICAL SOLVENT EFFECT THEORIES [J].
ANGYAN, JG .
JOURNAL OF MATHEMATICAL CHEMISTRY, 1992, 10 (1-4) :93-137
[4]  
[Anonymous], POLARIZABLE EMBEDDIN
[5]   ATOM DIPOLE INTERACTION MODEL FOR MOLECULAR POLARIZABILITY - APPLICATION TO POLYATOMIC-MOLECULES AND DETERMINATION OF ATOM POLARIZABILITIES [J].
APPLEQUIST, J ;
CARL, JR ;
FUNG, KK .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1972, 94 (09) :2952-+
[6]   DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].
BECKE, AD .
JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652
[7]   Benchmarking two-photon absorption cross sections: performance of CC2 and CAM-B3LYP [J].
Beerepoot, Maarten T. P. ;
Friese, Daniel H. ;
List, Nanna H. ;
Kongsted, Jacob ;
Ruud, Kenneth .
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2015, 17 (29) :19306-19314
[8]  
BOTCHER CJF, 1973, DIELECTRICS STATIC F, V1
[9]   An attempt to bridge the gap between computation and experiment for nonlinear optical properties: Macroscopic susceptibilities in solution? [J].
Cammi, R ;
Mennucci, B ;
Tomasi, J .
JOURNAL OF PHYSICAL CHEMISTRY A, 2000, 104 (20) :4690-4698
[10]   On the calculation of infrared intensities in solution within the polarizable continuum model [J].
Cammi, R ;
Cappelli, C ;
Corni, S ;
Tomasi, J .
JOURNAL OF PHYSICAL CHEMISTRY A, 2000, 104 (44) :9874-9879