Application of Multipolar Charge Models and Molecular Dynamics Simulations to Study Stark Shifts in Inhomogeneous Electric Fields

Devereux, Michael and Plattner, Nuria and Meuwly, Markus. (2009) Application of Multipolar Charge Models and Molecular Dynamics Simulations to Study Stark Shifts in Inhomogeneous Electric Fields. Journal of Physical Chemistry A, 113 (47). pp. 13199-13209.

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Official URL: https://edoc.unibas.ch/85121/

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Atomic multipole moments are used to investigate vibrational frequency shifts of CO and H(2) in uniform and inhomogeneous electric fields using ab initio calculations and Molecular Dynamics (MD) simulations. The importance of using atomic multipole moments that can accurately represent both molecular electrostatics and the vibrational response of the molecule to changes in the local electric field is highlighted. The vibrational response of CO to applied uniform and inhomogeneous electric fields is examined using Density Functional Theory calculations for a range of test fields, and the results are used to assess the performance of different atomic multipole models. In uniform fields, the calculated Stark tuning rates of Deltamu = 0.52 cm(-1)/(MV/cm) (DFT), Deltamu = 0.55 cm(-1)/(MV/cm) (fluctuating three-point charge model), and Deltamu = 0.64 cm(-1)/(MV/cm) (Multipole model up to octupole), compare favorably with the experimentally measured value of 0.67 cm(-1)/(MV/cm). For H(2), which has no permanent dipole moment, CCSD(T) calculations demonstrate the importance of bond-weakening effects in force fields in response to the applied inhomogeneous electric field. Finally, CO in hexagonal ice is considered as a test system to highlight the performance of selected multipolar models in MD simulations. The approach discussed here can be applied to calibrate a range of multipolar charge models for diatomic probes, with applications to interpret Stark spectroscopy measurements in protein active sites.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Physikalische Chemie (Meuwly)
UniBasel Contributors:Meuwly, Markus and Devereux, Michael
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:American Chemical Society
Note:Publication type according to Uni Basel Research Database: Journal article
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Last Modified:15 Nov 2021 16:24
Deposited On:15 Nov 2021 16:24

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