化学物理
We have developed a reduced-cost non-Dyson third-order algebraic diagrammatic construction theory for the electron-attachment problem based on state-specific frozen natural orbitals. Density fitting and truncated natural auxiliary functions…
We investigate an approximate sampling scheme that can significantly reduce the cost scaling of variational Monte Carlo when it is employed to predict the energy differences associated with local chemical changes. Inspired by side-chaining…
It seems self-evident that a density functional calculation should be normalized to the number of electrons in the system. We present multiple examples where the accuracy of the approximate energy is improved (sometimes greatly) by…
Nuclear quantum effects (NQEs) are often central to a predictive understanding of chemical reactions and rates. While their incorporation in gas-phase reactions is well established, studies involving condensed matter often neglect or…
The reaction dynamics of O(3P) + O2(3Sigma_g-) collisions in the O3(1A') electronic ground state is characterized on a high-level MRCI+Q/aug-cc-pVQZ potential energy surface represented as a reproducing kernel. For the atom exchange…
Recently, Ryu et al. showed that two broadened bands connected by a set of four Einstein-coefficient spectra for stimulated and spontaneous single-photon transitions will obey detailed balance at equilibrium if the spectra satisfy…
For decades, scientists have studied the intricate charge migration dynamics, where after ionization a localized charge distribution ("hole") migrates across the molecule on a femtosecond timescale. This has the potential for controlling…
A comparison of the {\it ab initio} calculations using the i-DMFT Method by Di Liu et al. (2025) with benchmark potential curves for three HX(F,Cl,Br) halides shows their inaccuracy in the domain around equilibrium - they do not reproduce…
We outline the design and characterization of a laser pulse shaper, which creates an ``ultraslow optical centrifuge'' - a linearly polarized field whose polarization vector rotates with arbitrarily low angular acceleration. By directly…
Molecular structure elucidation from spectroscopic data is a long-standing challenge in Chemistry, traditionally requiring expert interpretation. We introduce NMIRacle, a two-stage generative framework that builds upon recent paradigms in…
Understanding the mechanism of chemical reaction rate modulation by vibrational strong coupling (VSC) has been the focus of several recent studies. However, a definitive explanation for the mode-specificity of VSC still eludes us. In this…
We use optical-optical double-resonance (OODR) spectroscopy to measure for the first time hot-band transitions of ethylene (C${_2}$H${_4}$) between states in the 3000 cm$^{-1}$ and 9000 cm$^{-1}$ energy ranges. A 3.2 ${\mu}$m continuous…
Collective light-matter systems host an extensive manifold of dark states whose role in the emergence of thermodynamic behavior remains poorly understood, especially in the presence of disorder and structured environments. Here, we develop…
We use sub-Doppler optical-optical double-resonance (OODR) spectroscopy with a 3.3 ${\mu}$m single-frequency pump and a cavity-enhanced 1.65 ${\mu}$m comb probe to measure 33 ladder-type (3${\nu}$${_3}$ ${\leftarrow}$ ${\nu}$${_3}$) and 8…
The generation of unidirectional motion has been a long-standing challenge in engineering of molecular motors. Here, a mechanism driving the rotation is presented based on electron current through helical orbitals on a $\pi$-bonded carbon…
Hyperpolarisation using Signal Amplification By Reversible Exchange (SABRE) is a convenient method for high repeatability studies. The core of this technique is polarisation transfer to the target substrate during an on-going chemical…
Excited atoms and molecules can utilize their excess energy to ionize a neighboring system by a process named interatomic and intermolecular Coulombic decay (ICD). ICD is ultrafast, in the femtosecond regime, and has many modes of…
We define and calculate the triplet-pair population of the $2^1A_g$ dark state in polyenes, as predicted by the $\pi$-electron Pariser-Parr-Pople (PPP) model, for chains of 8 to 14 C-atoms and Coulomb interaction parameter between 4-14 eV.…
We compute highly accurate first principle based \textit{ab initio} adiabatic potential energy surfaces (PESs) using State-Averaged Multi-Configurational Self-Consistent Field (SA-MCSCF) followed by internally contracted Multi-Reference…
Quantitative prediction of thermodynamic properties in solution is essential for translating atomistic simulations into reliable chemical insight. As an exemplar system, the behaviour of CaCO$_3$ in water has been widely studied to…