skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Electronic Excitations in Complex Molecular Environments: Many-Body Green’s Functions Theory in VOTCA-XTP

Abstract

Many-body Green’s functions theory within the GW approximation and the Bethe-Salpeter Equation (BSE) is implemented in the open-source VOTCA-XTP software, aiming at the calculation of electronically excited states in complex molecular environments. Based on Gaussian-type atomic orbitals and making use of resolution of identity techniques, the code is designed specifically for nonperiodic systems. Application to a small molecule reference set successfully validates the methodology and its implementation for a variety of excitation types covering an energy range from 2 to 8 eV in single molecules. Further, embedding each GW-BSE calculation into an atomistically resolved surrounding, typically obtained from Molecular Dynamics, accounts for effects originating from local fields and polarization. Using aqueous DNA as a prototypical system, different levels of electrostatic coupling between the regions in this GW-BSE/MM setup are demonstrated. Particular attention is paid to charge-transfer (CT) excitations in adenine base pairs. It is found that their energy is extremely sensitive to the specific environment and to polarization effects. The calculated redshift of the CT excitation energy compared to a nucelobase dimer treated in vacuum is of the order of 1 eV, which matches expectations from experimental data. Predicted lowest CT energies are below that of a single nucleobase excitation,more » indicating the possibility of an initial (fast) decay of such an UV excited state into a binucleobase CT exciton. Furthermore, the results show that VOTCA-XTP’s GW-BSE/MM is a powerful tool to study a wide range of types of electronic excitations in complex molecular environments.« less

Authors:
 [1];  [2];  [3]; ORCiD logo [4];  [5];  [5];  [5];  [5]; ORCiD logo [5]
  1. Max Planck Institute for Polymer Research, Mainz (Germany); Eindhoven Univ. of Technology, Eindhoven (The Netherlands)
  2. Max Planck Institute for Polymer Research, Mainz (Germany)
  3. Univ. of Colorado, Boulder, CO (United States)
  4. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  5. Eindhoven Univ. of Technology, Eindhoven (The Netherlands)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA), Office of Defense Programs (DP) (NA-10)
OSTI Identifier:
1482949
Report Number(s):
LA-UR-18-25410
Journal ID: ISSN 1549-9618
Grant/Contract Number:  
89233218CNA000001
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Chemical Theory and Computation
Additional Journal Information:
Journal Volume: 14; Journal Issue: 12; Journal ID: ISSN 1549-9618
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Wehner, Jens, Brombacher, Lothar, Brown, Joshua, Junghans, Christoph, Çaylak, Onur, Khalak, Yuriy, Madhikar, Pranav, Tirimbò, Gianluca, and Baumeier, Björn. Electronic Excitations in Complex Molecular Environments: Many-Body Green’s Functions Theory in VOTCA-XTP. United States: N. p., 2018. Web. doi:10.1021/acs.jctc.8b00617.
Wehner, Jens, Brombacher, Lothar, Brown, Joshua, Junghans, Christoph, Çaylak, Onur, Khalak, Yuriy, Madhikar, Pranav, Tirimbò, Gianluca, & Baumeier, Björn. Electronic Excitations in Complex Molecular Environments: Many-Body Green’s Functions Theory in VOTCA-XTP. United States. doi:10.1021/acs.jctc.8b00617.
Wehner, Jens, Brombacher, Lothar, Brown, Joshua, Junghans, Christoph, Çaylak, Onur, Khalak, Yuriy, Madhikar, Pranav, Tirimbò, Gianluca, and Baumeier, Björn. Wed . "Electronic Excitations in Complex Molecular Environments: Many-Body Green’s Functions Theory in VOTCA-XTP". United States. doi:10.1021/acs.jctc.8b00617. https://www.osti.gov/servlets/purl/1482949.
@article{osti_1482949,
title = {Electronic Excitations in Complex Molecular Environments: Many-Body Green’s Functions Theory in VOTCA-XTP},
author = {Wehner, Jens and Brombacher, Lothar and Brown, Joshua and Junghans, Christoph and Çaylak, Onur and Khalak, Yuriy and Madhikar, Pranav and Tirimbò, Gianluca and Baumeier, Björn},
abstractNote = {Many-body Green’s functions theory within the GW approximation and the Bethe-Salpeter Equation (BSE) is implemented in the open-source VOTCA-XTP software, aiming at the calculation of electronically excited states in complex molecular environments. Based on Gaussian-type atomic orbitals and making use of resolution of identity techniques, the code is designed specifically for nonperiodic systems. Application to a small molecule reference set successfully validates the methodology and its implementation for a variety of excitation types covering an energy range from 2 to 8 eV in single molecules. Further, embedding each GW-BSE calculation into an atomistically resolved surrounding, typically obtained from Molecular Dynamics, accounts for effects originating from local fields and polarization. Using aqueous DNA as a prototypical system, different levels of electrostatic coupling between the regions in this GW-BSE/MM setup are demonstrated. Particular attention is paid to charge-transfer (CT) excitations in adenine base pairs. It is found that their energy is extremely sensitive to the specific environment and to polarization effects. The calculated redshift of the CT excitation energy compared to a nucelobase dimer treated in vacuum is of the order of 1 eV, which matches expectations from experimental data. Predicted lowest CT energies are below that of a single nucleobase excitation, indicating the possibility of an initial (fast) decay of such an UV excited state into a binucleobase CT exciton. Furthermore, the results show that VOTCA-XTP’s GW-BSE/MM is a powerful tool to study a wide range of types of electronic excitations in complex molecular environments.},
doi = {10.1021/acs.jctc.8b00617},
journal = {Journal of Chemical Theory and Computation},
issn = {1549-9618},
number = 12,
volume = 14,
place = {United States},
year = {2018},
month = {11}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Save / Share: