Subscribe to the gold package and get unlimited access to Shamra Academy
Register a new userOn the inclusion of cusp effects in expectation values with explicitly correlated Gaussians
95
0
0.0
(
0
)
Ask ChatGPT about the research
No Arabic abstract
This paper elaborates the integral transformation technique of [K. Pachucki, W. Cencek, and J. Komasa, J. Chem. Phys. 122, 184101 (2005)] and uses it for the case of the non-relativistic kinetic and Coulomb potential energy operators, as well as for the relativistic mass-velocity and Darwin terms. The techniques are tested for the ground electronic state of the helium atom and new results are reported for the ground electronic state of the H$_3^+$ molecular ion near its equilibrium structure.
rate research
Read More
We present a near-linear scaling formulation of the explicitly-correlated coupled-cluster singles and doubles with perturbative triples method (CCSD(T)$_{overline{text{F12}}}$) for high-spin states of open-shell species. The approach is based on the conventional open-shell CCSD formalism [M. Saitow et al., J. Chem. Phys. 146, 164105 (2017)] utilizing the domain local pair-natural orbitals (DLPNO) framework. The use of spin-independent set of pair-natural orbitals ensures exact agreement with the closed-shell formalism reported previously, with only marginally impact on the cost (e.g. the open-shell formalism is only 1.5 times slower than the closed-shell counterpart for the $text{C}_text{160}text{H}_{text{322}}$ n-alkane, with the measured size complexity of $approx1.2$). Evaluation of coupled-cluster energies near the complete-basis-set (CBS) limit for open-shell systems with more than 550 atoms and 5000 basis functions is feasible on a single multi-core computer in less than 3 days. The aug-cc-pVTZ DLPNO-CCSD(T)$_{overline{text{F12}}}$ contribution to the heat of formation for the 50 largest molecules among the 348 core combustion species benchmark set [J. Klippenstein et al., J. Phys. Chem. A 121, 6580 (2017)] had root-mean-square deviation (RMSD) from the extrapolated CBS CCSD(T) reference values of 0.3 kcal/mol. For a more challenging set of 50 reactions involving small closed- and open-shell molecules [G. Knizia et al., J. Chem. Phys. 130, 054104 (2009)] the aug-cc-pVQ(+d)Z DLPNO-CCSD(T)$_{overline{text{F12}}}$ yielded a RMSD of $sim$0.4 kcal/mol with respect to the CBS CCSD(T) estimate.
Understanding the asymptotic behavior of physical quantities in the thermodynamic limit is a fundamental problem in statistical mechanics. In this paper, we study how fast the eigenstate expectation values of a local operator converge to a smooth function of energy density as the system size diverges. In translationally invariant systems in any spatial dimension, we prove that for all but a measure zero set of local operators, the deviations of finite-size eigenstate expectation values from the aforementioned smooth function are lower bounded by $1/O(N)$, where $N$ is the system size. The lower bound holds regardless of the integrability or chaoticity of the model, and is tight in systems satisfying the eigenstate thermalization hypothesis.
We consider the transmission of a memoryless bivariate Gaussian source over an average-power-constrained one-to-two Gaussian broadcast channel. The transmitter observes the source and describes it to the two receivers by means of an average-power-constrained signal. Each receiver observes the transmitted signal corrupted by a different additive white Gaussian noise and wishes to estimate the source component intended for it. That is, Receiver~1 wishes to estimate the first source component and Receiver~2 wishes to estimate the second source component. Our interest is in the pairs of expected squared-error distortions that are simultaneously achievable at the two receivers. We prove that an uncoded transmission scheme that sends a linear combination of the source components achieves the optimal power-versus-distortion trade-off whenever the signal-to-noise ratio is below a certain threshold. The threshold is a function of the source correlation and the distortion at the receiver with the weaker noise.
The effect of conical intersections (CIs) on electronic relaxation, transitions from excited states to ground states, is well studied, but their influence on hyperfine quenching in a reactant molecule is not known. Here, we report on ultracold collision dynamics of the hydroxyl free-radical OH with Sr atoms leading to quenching of OH hyperfine states. Our quantum-mechanical calculations of this process reveal that quenching is efficient due to anomalous molecular dynamics in the vicinity of the conical intersection at collinear geometry. We observe wide scattering resonance features in both elastic and inelastic rate coefficients at collision energies below k x 10 mK. They are identified as either p- or d-wave shape resonances. We also describe the electronic potentials relevant for these non-reactive collisions, their diabatization procedure, as well as the non-adiabatic coupling between the diabatic potentials near the CIs.
Modeling linear absorption spectra of solvated chromophores is highly challenging as contributions are present both from coupling of the electronic states to nuclear vibrations and solute-solvent interactions. In systems where excited states intersect in the Condon region, significant non-adiabatic contributions to absorption lineshapes can also be observed. Here, we introduce a robust approach to model linear absorption spectra accounting for both environmental and non-adiabatic effects from first principles. This model parameterizes a linear vibronic coupling (LVC) Hamiltonian directly from energy gap fluctuations calculated along molecular dynamics (MD) trajectories of the chromophore in solution, accounting for both anharmonicity in the potential and direct solute-solvent interactions. The resulting system dynamics described by the LVC Hamiltonian are solved exactly using the thermalized time-evolving density operator with orthogonal polynomials algorithm (T-TEDOPA). The approach is applied to the linear absorption spectrum of methylene blue (MB) in water. We show that the strong shoulder in the experimental spectrum is caused by vibrationally driven population transfer between the bright S1 and the dark S2 state. The treatment of the solvent environment is one of many factors which strongly influences the population transfer and lineshape; accurate modeling can only be achieved through the use of explicit quantum mechanical solvation. The efficiency of T-TEDOPA, combined with LVC Hamiltonian parameterizations from MD, leads to an attractive method for describing a large variety of systems in complex environments from first principles.
Log in to be able to interact and post comments
comments
Fetching comments
Sign in to be able to follow your search criteria
