How Reliable Are Modern Density Functional Approximations to Simulate Vibrational Spectroscopies?

We show that properties of molecules with low-frequency modes calculated with density functional approximations (DFAs) suffer from spurious oscillations along the nuclear displacement coordinate due to numerical integration errors. Occasionally, the problem can be alleviated using extensive integration grids that compromise the favorable cost-accuracy ratio of DFAs. Since spurious oscillations are difficult to predict or identify, DFAs are exposed to severe performance errors in IR and Raman intensities and frequencies or vibrational contributions to any molecular property. Using Fourier spectral analysis and digital signal processing techniques, we identify and quantify the error due to these oscillations for 45 widely used DFAs. LC-BLYP and BH&H are revealed as the only functionals showing robustness against the spurious oscillations of various energy, dipole moment, and polarizability derivatives with respect to a nuclear displacement coordinate. Given the ubiquitous nature of molecules with low-frequency modes, we warrant caution in using modern DFAs to simulate vibrational spectroscopies.This paper is dedicated to Gernot Frenking on occasion of his 75th birthday. Grants PGC2018-098212-B-C21, PGC2018- 098212-B-C22, and IJCI-2017-34658 funded by MCIN/AEI/ 10.13039/501100011033 and “FEDER Una manera de hacer Europa”, and the grants funded by Diputación Foral de Gipuzkoa (Grant 2019-CIEN-000092-01), and Gobierno Vasco (Grants IT1254-19, PRE_2020_2_0015, and PIBA19- 0004) are acknowledged. R.Z. gratefully acknowledges support from the Polish National Science Center (Grant 2018/30/E/ ST4/00457)

Choosing Bad versus Worse: Predictions of Two-Photon-Absorption Strengths Based on Popular Density Functional Approximations

We present a benchmark study of density functional approximation (DFA) performances in predicting the two-photon-absorption strengths in π-conjugated molecules containing electron-donating/-accepting moieties. A set of 48 organic molecules is chosen for this purpose, for which the two-photon-absorption (2PA) parameters are evaluated using different DFAs, including BLYP, PBE, B3LYP, PBE0, CAM-B3LYP, LC-BLYP, and optimally tuned LC-BLYP. Minnesota functionals and ωB97X-D are also used, applying the two-state approximation, for a subset of molecules. The efficient resolution-of-identity implementation of the coupled-cluster CC2 model (RI-CC2) is used as a reference for the assessment of the DFAs. Two-state models within the framework of both DFAs and RI-CC2 are used to gain a deeper insight into the performance of different DFAs. Our results give a clear picture of the performance of the density functionals in describing the two-photon activity in dipolar π-conjugated systems. The results show that global hybrids are best suited to reproduce the absolute values of 2PA strengths of donor–acceptor molecules. The range-separated functionals CAM-B3LYP and optimally tuned LC-BLYP, however, show the highest linear correlations with the reference RI-CC2 results. Hence, we recommend the latter DFAs for structure–property studies across large series of dipolar compounds

Spurious Oscillations Caused by Density Functional Approximations: Who is to Blame? Exchange or Correlation?

We analyze the varying susceptibilities of different density functional approximations (DFAs) to present spurious oscillations on the profiles of several vibrational properties. Among other problems, these spurious oscillations cause significant errors in harmonic and anharmonic IR and Raman frequencies and intensities. This work hinges on a judicious strategy to dissect the exchange and correlation components of DFAs and pinpoint the origins of these oscillations. We identify spurious oscillations in derivatives of all energy components with respect to nuclear displacements, including those energy terms that do not involve numerical integrations. These indirect spurious oscillations are attributed to suboptimal electron densities resulting from a self-consistent field procedure using a DFA that exhibits direct spurious oscillations. Direct oscillations stem from inaccurate numerical integration of the exchange and correlation energy density functionals. A thorough analysis of direct spurious oscillations reveals that only a handful of exchange and correlation components are insensitive to spurious oscillations, giving rise to three families of functionals, BH&H, LSDA, and BLYP. Among the functionals in these families, we encounter four widespread DFAs: BLYP, B3LYP, LC-BLYP, and CAM-B3LYP. Certain DFAs like PBE appear less sensitive to spurious oscillations due to compensatory cancellations between their energy components. Additionally, we found non-negligible but small oscillations in PBE and TPSS, which could be safely employed provided a sufficiently large integration grid is used in the calculations. These findings hint at the key components of current approximations to be improved and emphasize the necessity to develop accurate DFAs suitable for studying molecular spectroscopies

Ab initio quantum-chemical computations of the electronic states in HgBr2 and IBr: Molecules of interest on the Earth’s atmosphere

The electronic states of atmospheric relevant molecules IBr and HgBr2 are reported, within the UV-Vis spectrum range (170nm≤λphoton≤600 nm) by means of the complete-active-space self-consistent field/multi-state complete-active-space second-order perturbation theory/spin-orbit restricted-active-space state-interaction (CASSCF/MS-CASPT2/SO-RASSI) quantum-chemical approach and atomic-natural-orbital relativistic-correlation-consistent (ANO-RCC) basis sets. Several analyses of the methodology were carried out in order to reach converged results and therefore to establish a highly accurate level of theory. Good agreement is found with the experimental data with errors not higher than around 0.1 eV. The presented analyses shall allow upcoming studies aimed to accurately determine the absorption cross sections of interhalogen molecules and compounds with Hg that are relevant to better comprehend the photochemical processes taking place in the atmosphere.Fil: Sitkiewicz, Sebastian P.. Universidad de Valencia; EspañaFil: Oliva, Josep M.. Consejo Superior de Investigaciones Científicas. Instituto de Química Física; EspañaFil: Dávalos, Juan Z.. Consejo Superior de Investigaciones Científicas. Instituto de Química Física; EspañaFil: Notario, Rafael. Consejo Superior de Investigaciones Científicas. Instituto de Química Física; EspañaFil: Saiz-Lopez, Alfonso. Consejo Superior de Investigaciones Científicas. Instituto de Química Física; EspañaFil: Alcoba, Diego Ricardo. Universidad de Buenos Aires; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Física de Buenos Aires. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Física de Buenos Aires; ArgentinaFil: Oña, Ofelia Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Roca-Sanjuán, Daniel. Universidad de Valencia; Españ