化学物理

Characterization of the structural and electron transport properties of single chiral molecules provides critical insights into the interplay between their electronic structure and electrochemical environments, providing broader…

The nitrate radical NO$_3$ plays an important role in atmospheric chemistry, yet many aspects of its coupled and anharmonic vibronic structure remain elusive. Here, using an accurate, coupled full-dimensional diabatic potential that…

The long-time behavior of many complex molecular systems is often governed by slow relaxation dynamics that can be described by a few reaction coordinates referred to as collective variables (CVs). However, identifying CVs hidden in a…

Despite its simplicity, the single-trajectory thawed Gaussian approximation has proven useful for calculating vibrationally resolved electronic spectra of molecules with weakly anharmonic potential energy surfaces. Here, we show that the…

Under certain conditions, the ionization of a molecule may create a superposition of electronic states, leading to ultrafast electron dynamics. If controlled, this motion could be used in attochemistry applications, but it has been shown…

It is well known that the association of parahydrogen (pH2) with an unsaturated molecule or a transient metalorganic complex can enhance the intensity of NMR signals; the effect is known as parahydrogen-induced polarization (PHIP). During…

Using a combination of high-level ab initio electronic structure methods with efficient on-the-fly semiclassical evaluation of nuclear dynamics, we performed a massive scan of small polyatomic molecules searching for a long lasting…

The explicit split-operator algorithm is often used for solving the linear and nonlinear time-dependent Schr\"{o}dinger equations. However, when applied to certain nonlinear time-dependent Schr\"{o}dinger equations, this algorithm loses…

We describe a new method for pulsed spin order transfer (SOT) of parahydrogen induced polarization (PHIP) that enables close to 100 % polarization in incompletely 2H-labeled molecules by exciting only the desired protons in a…

Accurate description of finite-temperature vibrational dynamics is indispensable in the computation of two-dimensional electronic spectra. Such simulations are often based on the density matrix evolution, statistical averaging of initial…

Choosing an appropriate representation of the molecular Hamiltonian is one of the challenges faced by simulations of the nonadiabatic quantum dynamics around a conical intersection. The adiabatic, exact quasidiabatic, and strictly diabatic…

Ab initio computation of two-dimensional electronic spectra is an expanding field, whose goal is improving upon simple, few-dimensional models often employed to explain experiments. Here, we propose an accurate and computationally…

The explicit split-operator algorithm has been extensively used for solving not only linear but also nonlinear time-dependent Schr\"{o}dinger equations. When applied to the nonlinear Gross-Pitaevskii equation, the method remains…

To compute and analyze vibrationally resolved electronic spectra at zero temperature, we have recently implemented the on-the-fly ab initio extended thawed Gaussian approximation [A. Patoz et al., J. Phys. Chem. Lett. 9, 2367 (2018)], which…

Azulene is a prototypical molecule with an anomalous fluorescence from the second excited electronic state, thus violating Kasha's rule, and with an emission spectrum that cannot be understood within the Condon approximation. To better…

Path integral calculations of equilibrium isotope effects and isotopic fractionation are expensive due to the presence of path integral discretization errors, statistical errors, and thermodynamic integration errors. Whereas the…

Exact nonadiabatic quantum evolution preserves many geometric properties of the molecular Hilbert space. In a companion paper [S. Choi and J. Van\'{\i}\v{c}ek, 2019], we presented numerical integrators of arbitrary-order of accuracy that…

Geometric integrators of the Schr\"{o}dinger equation conserve exactly many invariants of the exact solution. Among these integrators, the split-operator algorithm is explicit and easy to implement, but, unfortunately, is restricted to…

To alleviate the computational cost associated with on-the-fly ab initio semiclassical calculations of molecular spectra, we propose the single-Hessian thawed Gaussian approximation, in which the Hessian of the potential energy at all…

In this paper, we propose a novel flexible optimization pipeline for determining the optimal adsorption sites, named AUGUR (Aware of Uncertainty Graph Unit Regression). Our model combines graph neural networks and Gaussian processes to…