English (United Kingdom)

https://curated-unify.zendy.io/wp-json/zendy-region/v1/featured_content/oa?rat=en

https://curated-unify.zendy.io/wp-json/zendy-region/v1/highlighted_journal/

Global: Zendy Plus annual

Presents the access of premium content as premium feature

Premium Content

Presents the keyphrase highlighting as premium feature

Keyphrase Highlighting

Presents the summarisation as premium feature

Summarisation

Insights

Presents the pdf analysis as premium feature

PDF Analysis

Presents the zaia usage as premium feature

ZAIA

Global: Zendy Tools annual

Global: Zendy Free Plan

Global: Zendy Tools monthly

Global: Zendy Plus monthly

The third-order response lies at the heart of simulating and interpretingnonlinear spectroscopies ranging from two dimensional infrared (2D-IR) to 2Delectronic (2D-ES), and 2D sum frequency generation (2D-SFG). The extra timeand frequency dimensions in these spectroscopies provides access to richinformation on the electronic and vibrational states present, the couplingbetween them, and the resulting rates at which they exchange energy that areobscured in linear spectroscopy, particularly for condensed phase systems thatusually contain many overlapping features. While the exact quantum expressionfor the third-order response is well established it is incompatible with themethods that are practical for calculating the atomistic dynamics of largecondensed phase systems. These methods, which include both classical mechanicsand quantum dynamics methods that retain quantum statistical properties whileobeying the symmetries of classical dynamics, such as LSC-IVR, CentroidMolecular Dynamics (CMD) and Ring Polymer Molecular Dynamics (RPMD) naturallyprovide short-time approximations to the multi-time symmetrized Kubotransformed correlation function. Here, we show how the third-order responsecan be formulated in terms of equilibrium symmetrized Kubo transformedcorrelation functions. We demonstrate the utility and accuracy of our approachby showing how it can be used to obtain the third-order response of a series ofmodel systems using both classical dynamics and RPMD. In particular, we showthat this approach captures features such as anharmonically induced verticalsplittings and peak shifts while providing a physically transparent frameworkfor understanding multidimensional spectroscopies.

2D spectroscopies from condensed phase dynamics: Accessing third-order response properties from equilibrium multi-time correlation functions