TY - JOUR

T1 - Electric Properties of Photochromic Molecules Physisorbed on Silver and Copper Nanoparticles

AU - Hillers-Bendtsen, Andreas Erbs

AU - Kjeldal, Frederik Ørsted

AU - Mikkelsen, Kurt V.

N1 - Funding Information: This work was supported by the Center for Exploitation of Solar Energy, Department of Chemistry, University of Copenhagen, Denmark, and the Danish e-Infrastructure Cooperation. A.E.H.-B. and F.Ø.K. thank the Danish Chemical Society for travel support to Pennsylvania State University. Publisher Copyright: © 2022 American Chemical Society. All rights reserved.

PY - 2022

Y1 - 2022

N2 - This paper investigates the electric properties of the photochromic dihydroazulene/vinylheptafulvene system as it is physisorbed onto silver and copper nanoparticles. Our focus is on how the polarizability and hyperpolarizability of the dihydroazulene, s-cis-vinylheptafulvene, and s-trans-vinylheptafulvene molecules depend on molecular orientation with respect to the nanoparticles, the molecule-cluster separation, and the type of nanoparticle. The computational approach utilizes a combined quantum mechanical/molecular mechanical method in which the molecules are treated quantum mechanically while the nanoparticles are treated with a simpler classical method. The molecules are described with density functional theory. The electric properties are calculated using response theory utilizing the long-range-corrected functional CAM-B3LYP and the correlation consistent basis set aug-cc-pVDZ. The atoms of the nanoparticles are represented using atomic polarizabilities. The interactions between the nanoparticles and the molecular systems are calculated using a polarizable embedding scheme after which the molecular properties are calculated with time-dependent density functional theory. The results show that the electric properties are indeed affected by the presence of the nanoparticles. It is also clear that it is the hyperpolarizabilities that change the most while the polarizabilities are less affected. Furthermore, the influence of the nanoparticles on the molecules depends heavily on the relative molecular orientation with respect to the nanoparticles and molecular conformation. Finally, it is observed that a copper nanoparticle has a larger influence on the molecular systems than a silver nanoparticle.

AB - This paper investigates the electric properties of the photochromic dihydroazulene/vinylheptafulvene system as it is physisorbed onto silver and copper nanoparticles. Our focus is on how the polarizability and hyperpolarizability of the dihydroazulene, s-cis-vinylheptafulvene, and s-trans-vinylheptafulvene molecules depend on molecular orientation with respect to the nanoparticles, the molecule-cluster separation, and the type of nanoparticle. The computational approach utilizes a combined quantum mechanical/molecular mechanical method in which the molecules are treated quantum mechanically while the nanoparticles are treated with a simpler classical method. The molecules are described with density functional theory. The electric properties are calculated using response theory utilizing the long-range-corrected functional CAM-B3LYP and the correlation consistent basis set aug-cc-pVDZ. The atoms of the nanoparticles are represented using atomic polarizabilities. The interactions between the nanoparticles and the molecular systems are calculated using a polarizable embedding scheme after which the molecular properties are calculated with time-dependent density functional theory. The results show that the electric properties are indeed affected by the presence of the nanoparticles. It is also clear that it is the hyperpolarizabilities that change the most while the polarizabilities are less affected. Furthermore, the influence of the nanoparticles on the molecules depends heavily on the relative molecular orientation with respect to the nanoparticles and molecular conformation. Finally, it is observed that a copper nanoparticle has a larger influence on the molecular systems than a silver nanoparticle.

U2 - 10.1021/acs.jpca.2c01003

DO - 10.1021/acs.jpca.2c01003

M3 - Journal article

C2 - 35583037

AN - SCOPUS:85131107073

VL - 126

SP - 3145

EP - 3156

JO - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

JF - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

SN - 1089-5639

IS - 20

ER -