Partitioning of interaction-induced nonlinear optical properties of molecular complexes. II. Halogen-bonded systems

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61989592%3A15310%2F20%3A73604320" target="_blank" >RIV/61989592:15310/20:73604320 - isvavai.cz</a>

Výsledek na webu

<a href="https://pubs.rsc.org/en/content/articlehtml/2020/cp/c9cp06620a" target="_blank" >https://pubs.rsc.org/en/content/articlehtml/2020/cp/c9cp06620a</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/c9cp06620a" target="_blank" >10.1039/c9cp06620a</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Partitioning of interaction-induced nonlinear optical properties of molecular complexes. II. Halogen-bonded systems

Popis výsledku v původním jazyce

Following our study on hydrogen-bonded (HB) complexes [Phys. Chem. Chem. Phys., 2018, 20, 19841], the physical nature of interaction-induced (non)linear optical properties of another important class of molecular complexes, namely halogen-bonded (XB) systems, was analyzed in this study. The excess electronic and nuclear relaxation (hyper)polarizabilities of nine representative XB complexes covering a wide range of halogen-bond strengths were computed. The partitioning of the excess properties into individual interaction-energy components (electrostatic, exchange, induction, dispersion) was performed by using the variational-perturbational energy decomposition scheme at the MP2/aug-cc-pVTZ level of theory and further supported by calculations with the SCS-MP2 method. In the case of the electronic interaction-induced properties, the physical composition of Delta alpha(el) and Delta gamma(el) was found to be very similar for the two types of bonding, despite the different nature of the binding. For Delta beta(el), the XB complexes exhibit a more systematic interplay of interaction-energy contributions compared to the HB systems studied in the previous work. Our analysis revealed that the patterns of interaction-energy contributions to the interaction-induced nuclear-relaxation contributions to the linear polarizability and the first hyperpolarizability are very similar. For both properties the exchange repulsion term is canceled out by the electrostatic and delocalization terms. The physical composition of these contributions is analogous to those observed for the HB complexes.

Název v anglickém jazyce

Partitioning of interaction-induced nonlinear optical properties of molecular complexes. II. Halogen-bonded systems

Popis výsledku anglicky

Following our study on hydrogen-bonded (HB) complexes [Phys. Chem. Chem. Phys., 2018, 20, 19841], the physical nature of interaction-induced (non)linear optical properties of another important class of molecular complexes, namely halogen-bonded (XB) systems, was analyzed in this study. The excess electronic and nuclear relaxation (hyper)polarizabilities of nine representative XB complexes covering a wide range of halogen-bond strengths were computed. The partitioning of the excess properties into individual interaction-energy components (electrostatic, exchange, induction, dispersion) was performed by using the variational-perturbational energy decomposition scheme at the MP2/aug-cc-pVTZ level of theory and further supported by calculations with the SCS-MP2 method. In the case of the electronic interaction-induced properties, the physical composition of Delta alpha(el) and Delta gamma(el) was found to be very similar for the two types of bonding, despite the different nature of the binding. For Delta beta(el), the XB complexes exhibit a more systematic interplay of interaction-energy contributions compared to the HB systems studied in the previous work. Our analysis revealed that the patterns of interaction-energy contributions to the interaction-induced nuclear-relaxation contributions to the linear polarizability and the first hyperpolarizability are very similar. For both properties the exchange repulsion term is canceled out by the electrostatic and delocalization terms. The physical composition of these contributions is analogous to those observed for the HB complexes.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2020

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Physical Chemistry Chemical Physics

ISSN

1463-9076

e-ISSN

—

Svazek periodika

22

Číslo periodika v rámci svazku

7

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

10

Strana od-do

4225-4234

Kód UT WoS článku

000518624400049

EID výsledku v databázi Scopus

2-s2.0-85080107502