Multireference nature of chemistry: the coupled-cluster view.

The computational bottleneck of the extremely fast simplified Tamm-Dancoff approximated (sTDA) time-dependent density functional theory procedure [S. Grimme, J. Chem. Phys. 138, 244104 (2013)] for the computation of electronic spectra for large systems is the determination of the ground state Kohn-Sham orbitals and eigenvalues. This limits such treatments to single structures with a few hundred atoms and hence, e.g., sampling along molecular dynamics trajectories for flexible systems or the calculation of chromophore aggregates is often not possible. The aim of this work is to solve this problem by a specifically designed semi-empirical tight binding (TB) procedure similar to the well established self-consistent-charge density functional TB scheme. The new special purpose method provides orbitals and orbital energies of hybrid density functional character for a subsequent and basically unmodified sTDA procedure. Compared to many previous semi-empirical excited state methods, an advantage of the ansatz is that a general eigenvalue problem in a non-orthogonal, extended atomic orbital basis is solved and therefore correct occupied/virtual orbital energy splittings as well as Rydberg levels are obtained. A key idea for the success of the new model is that the determination of atomic charges (describing an effective electron-electron interaction) and the one-particle spectrum is decoupled and treated by two differently parametrized Hamiltonians/basis sets. The three-diagonalization-step composite procedure can routinely compute broad range electronic spectra (0-8 eV) within minutes of computation time for systems composed of 500-1000 atoms with an accuracy typical of standard time-dependent density functional theory (0.3-0.5 eV average error). An easily extendable parametrization based on coupled-cluster and density functional computed reference data for the elements H-Zn including transition metals is described. The accuracy of the method termed sTDA-xTB is first benchmarked for vertical excitation energies of open- and closed-shell systems in comparison to other semi-empirical methods and applied to exemplary problems in electronic spectroscopy. As side products of the development, a robust and efficient valence electron TB method for the accurate determination of atomic charges as well as a more accurate calculation scheme of dipole rotatory strengths within the Tamm-Dancoff approximation is proposed.

Ultra-fast computation of electronic spectra for large systems by tight-binding based simplified Tamm-Dancoff approximation (sTDA-xTB).

The recently introduced sTDA methodology [S Grimme, J Chem Phys, 2013, 138, 244104] to compute excitation spectra of huge molecular systems is extended to range-separated hybrid (RSH) density functionals The three empirical parameters of the method which describe a screened two-electron interaction are obtained for some common RSH functionals (ωB97 family, CAM-B3LYP, LC-BLYP) from a fit to theoretical SCS-CC2 reference vertical excitation energies for a set of small to medium-sized chromophores The method is cross-validated on a set of inter- and intramolecular charge transfer states and a set composed of typical valence transitions Overall small deviations from reference data of only about 02–04 eV are found with best performance for CAM-B3LYP and ωB97X-D3 To demonstrate versatility and robustness of the new methodology, applications (the UV/Vis spectrum of the pyridine polymer and the ECD spectrum of (P)-[11]helicene) and frequently used charge transfer examples are discussed In one case, 11 000+ excited electronic states of a system containing 330 atoms were calculated We show that the asymptotically correct sTDA–RSH combination yields results often superior to those based on global hybrids and that it opens up new possibilities for the computation of excited states in materials science and bio-molecular systems

Excited states using the simplified Tamm-Dancoff-Approach for range-separated hybrid density functionals: development and application.

A new hierarchy of augmented basis sets optimized for the calculation of molecular properties such as indirect spin-spin coupling constants is presented. Based on the Dunning hierarchy of cc-pVXZ (X=D, T, Q, and 5) basis sets augmentation functions with tight exponents have been optimized for coupled-cluster calculations of indirect spin-spin coupling constants. The optimal exponents for these tight functions have been obtained by optimizing the sum of the absolute values of all contributions to the coupling constant. On the basis of a series of test cases (CO, HF, N2, F2, H2O, NH3, and CH4) we propose a set of tight s, p, and d functions to be added to the uncontracted Dunning basis sets, and, subsequently, to recontract. The resulting ccJ-pVXZ (X=D, T, Q, and 5) basis sets demonstrate excellent cost efficiency in benchmark calculations. These new basis sets should generally be applicable for the calculation of spin-spin coupling constants and other properties that have a strong dependence on powers of 1...

Optimization of augmentation functions for correlated calculations of spin-spin coupling constants and related properties

The state specific equation of motion coupled cluster (SS-EOMCC) method is an internally contracted multireference approach, applicable to both ground and excited states. Attractive features of the method are as follows: (1) the SS-EOMCC wave function is qualitatively correct and rigorously spin adapted, (2) both orbitals and dynamical correlation are optimized for the target state, (3) nondynamical correlation and differential orbital relaxation effects are taken care of by a diagonalization of the transformed Hamiltonian in the multireference configuration-interaction singles space, (4) only one- and two-particle density matrices of a complete-active-space self-consistent-field reference state are needed to define equations for the cluster amplitudes, and (5) the method is invariant with respect to orbital rotations in core, active, and virtual subspaces. Prior applications focused on biradical-like systems, in which only one extra orbital is needed to construct the active space, and similarly, single b...

State specific equation of motion coupled cluster method in general active space.

The rigorously size-extensive intruder-free state-specific multi-reference coupled cluster theory (SSMRCC) developed by Mukherjee and coworkers [J. Chem. Phys. 110 (1999) 6171] makes use of the Jeziorski–Monkhorst Ansatz [ Ω = ∑ μ exp ( T μ ) | ϕ μ 〉 〈 ϕ μ | ] involving a different cluster operator exp(Tμ) acting on its corresponding model function ϕμ. The resulting equations involve a coupling between the cluster operators for all the μ as demanded by the rigorous requirement of size-extensivity. If one wishes a size-extensive formalism where such couplings are minimal, one will have to replace the exact coupling term by hand where only Tμ for a given ϕμ appears. In this paper, we propose such an externally corrected size-extensive single-root multi-reference CC (ecsr-MRCC) formalism, which is intruder-free and simpler in structure as compared to the parent SSMRCC theory. Our intention in this paper is not to replace or underplay the efficacy of the rigorous SSMRCC theory, but to indicate how a simple external correction leads to results of similar quality where the coupling of Tμs for various μ are avoided. Kinship of the ecsr-MRCC formalism with the parent SSMRCC, and certain other allied MRCC theories will also be discussed. The performance of the method will be assessed by applying it to H4, BeH2, F2 and CH2, and comparing them against the SSMRCC results, benchmark full CI results (when available), and those from the allied MRCC formalisms. The encouraging results indicate that this simple modification leads to equations with the minimal coupling without unduly sacrificing the accuracy.

An externally-corrected size-extensive single-root MRCC formalism: its kinship with the rigorously size-extensive state-specific MRCC theory

A charged particle moving in a harmonic, symmetric double well, a square well, or a Morse potential is allowed to interact with a discontinuously reversing spatially homogeneous electric field. Randomly reversing field is seen to cause localization in the quantum system. A critical reversal frequency is seen to exist below which no localization is manifested in the harmonic, double and square well. In the Morse case, there is dissociation if the upper limit of the interval between random kicks exceeds τmax. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010

Localization in some discontinuously and randomly driven quantum systems

Coherent destruction of tunneling with optimally designed polychromatic external field

A zeroth-order, non-diffracting Bessel beam, generated by picosecond laser pulses (1064 nm, 10 Hz, 30 ps) through an axicon, was utilized to perform pulse energy-dependent (12 mJ, 16 mJ, 20 mJ, 24 mJ) laser ablation of silver (Ag) substrates in air. The fabrication resulted in finger-like Ag nanostructures (NSs) in the sub-200 nm domain and obtained structures were characterized using the FESEM and AFM techniques. Subsequently, we employed those Ag NSs in surface-enhanced Raman spectroscopy (SERS) studies achieving promising sensing results towards trace-level detection of six different hazardous materials (explosive molecules of picric acid (PA) and ammonium nitrate (AN), a pesticide thiram (TH) and the dye molecules of Methylene Blue (MB), Malachite Green (MG), and Nile Blue (NB)) along with a biomolecule (hen egg white lysozyme (HEWL)). The remarkably superior plasmonic behaviour exhibited by the AgNS corresponding to 16 mJ pulse ablation energy was further explored. To accomplish a real-time application-oriented understanding, time-dependent studies were performed utilizing the AgNS prepared with 16 mJ and TH molecule by collecting the SERS data periodically for up to 120 days. The coated AgNSs were prepared with optimized gold (Au) deposition, accomplishing a much lower trace detection in the case of thiram (~50 pM compared to ~50 nM achieved prior to the coating) as well as superior EF up to ~108 (~106 before Au coating). Additionally, these substrates have demonstrated superior stability compared to those obtained before Au coating.

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Subhasree Ghosh

Papers

An externally-corrected size-extensive single-root MRCC formalism: its kinship with the rigorously size-extensive state-specific MRCC theory

Localization in some discontinuously and randomly driven quantum systems

Coherent destruction of tunneling with optimally designed polychromatic external field

Picosecond Bessel Beam Fabricated Pure, Gold-Coated Silver Nanostructures for Trace-Level Sensing of Multiple Explosives and Hazardous Molecules

Bichromatic fluctuations in symmetric double well potentials: Localization and control of tunneling