Adaptive density-guided approach to double incremental potential energy surface construction

Artiukhin, Denis G.; Klinting, Emil Lund; König, Carolin; Christiansen, Ove

doi:10.1063/5.0004686

Cited by 11 publications

(13 citation statements)

References 78 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Although the largest of such molecular systems have only been treated at the level of two-mode couplings, while using low-accuracy electronic structure methods, recent progress indicates that high-accuracy computations can be made feasible. This includes developments in integration of machine learning techniques and double incremental expansion methods , for PES construction and tensor decomposition methods for anharmonic wave function calculations. These prospects also apply to the use of PsCs and potentially extends the impact of their utilization beyond the scope of the present work.…”

Section: Discussionmentioning

confidence: 99%

Vibrational Coupled Cluster Computations in Polyspherical Coordinates with the Exact Analytical Kinetic Energy Operator

Klinting

Lauvergnat

Christiansen

2020

J. Chem. Theory Comput.

Self Cite

View full text Add to dashboard Cite

We present the first use of curvilinear vibrational coordinates, specifically polyspherical coordinates, in combination with vibrational coupled cluster theory. The polyspherical coordinates are used in the context of both the adaptive density-guided approach to potential energy surface construction and in the subsequent vibrational coupled cluster calculations of anharmonic vibrational states. Results obtained based on the polyspherical coordinate parametrization are compared to results obtained with the use of rectilinear vibrational coordinates, namely normal coordinates and hybrid optimized and localized coordinates for the formaldehyde molecule. This comparison is carried out with the full vibrational configuration interaction model, using the respective fully coupled potential energy surfaces and untruncated kinetic energy operators. The polyspherical coordinates are shown to facilitate an acceleration of convergence for truncated methods, when compared to the use of normal coordinates. We furthermore report on calculations on the hydrogen peroxide molecule in polyspherical coordinate 1 parametrization. The polyspherical vibrational coordinates are shown to perform very well, even for truncated methods, especially when considering the difficulty that rectilinear vibrational coordinates can exhibit in treating complicated internal molecular motion.

show abstract

Section: Discussionmentioning

confidence: 99%

Vibrational Coupled Cluster Computations in Polyspherical Coordinates with the Exact Analytical Kinetic Energy Operator

Klinting

Lauvergnat

Christiansen

2020

J. Chem. Theory Comput.

Self Cite

View full text Add to dashboard Cite

show abstract

“…The concrete realization of the general idea pursued here is what we term the time-dependent adaptive density-guided approach (TD-ADGA) for PES construction. The TD-ADGA is a time-dependent generalization of the adaptive density-guided approach (ADGA) − that has been applied for more than a decade for constructing PESs for anharmonic vibrational computations. Essential to the ADGA approach is the concept of adaptively constructing the PES.…”

Section: Introductionmentioning

confidence: 99%

Quasi-direct Quantum Molecular Dynamics: The Time-Dependent Adaptive Density-Guided Approach for Potential Energy Surface Construction

Høyer,

Christiansen

2024

J. Chem. Theory Comput.

Self Cite

View full text Add to dashboard Cite

We present a new quasi-direct quantum molecular dynamics computational method which offers a compromise between quantum dynamics using a precomputed potential energy surface (PES) and fully direct quantum dynamics. This method is termed the time-dependent adaptive density-guided approach (TD-ADGA) and is a method for constructing a PES on the fly during a dynamics simulation. This is achieved by acquisition of new single-point (SP) calculations and refitting of the PES, depending on the need of the dynamics. The TD-ADGA is a further development of the adaptive density-guided approach (ADGA) for PES construction where the placement of SPs is guided by the density of the nuclear wave function. In TD-ADGA, the ADGA framework has been integrated into the time propagation of the time-dependent nuclear wave function and we use the reduced one-mode density of this wave function to guide when and where new SPs are placed. The PES is thus extended or updated if the wave function moves into new areas or if a certain area becomes more important. Here, we derive equations for the reduced one-mode density for the timedependent Hartree (TDH) method and for multiconfiguration time-dependent Hartree (MCTDH) methods, but the TD-ADGA can be used with any time-dependent wave function method as long as a density is available. The TD-ADGA method has been investigated on molecular systems containing single-and double-minimum potentials and on single-mode and multi-mode systems. We explore different approaches to handle the fact that the TD-ADGA involves a PES that changes during the computation and show how results can be obtained that are in very good agreement with results obtained by using an accurate reference PES. Dynamics with TD-ADGA is essentially a black box procedure, where only the initialization of the system and how to compute SPs must be provided. The TD-ADGA thus makes it easier to carry out quantum molecular dynamics and the quasi-direct framework opens up the possibility to compute quantum dynamics accurately for larger molecular systems.

show abstract

“…In particular, we will employ subsystem time-dependent densityfunctional theory [32][33][34][35] (subsystem TDDFT) with parallel FDE calculations as a reference [36,37] to efficiently obtain excited states. Besides the presented example, this massively-parallel framework could be employed to efficiently perform tasks such as embarrassingly-parallel potential-energy surface constructions [38][39][40][41][42][43], parallel mode-and intensity-tracking or general semi-numerical frequency calculations [44][45][46][47], or many-body expansion calculations [48][49][50][51][52].…”

Section: Introductionmentioning

confidence: 99%

Massively Parallel Fragment-Based Quantum Chemistry for Large Molecular Systems: The Serestipy Software

Eschenbach

Niemeyer

Neugebauer

2022

Preprint

View full text Add to dashboard Cite

We describe the Serestipy software, which is an add-on to the quantum-chemistry program Serenity. Serestipy is a representational-state transfer-oriented application programming interface written in the Python programming language enabling parallel subsystem density-functional theory calculations. We introduce approximate strategies in the context of frozen-density embedding time-dependent density-functional theory to make parallel large-scale excited-state calculations feasible. Their accuracy is carefully benchmarked with calculations for large assemblies of porphine molecules. We apply this framework to a theoretical model nanotube consisting of rings of porphine monomers, with 12,160 atoms (or 264,960 basis functions) in total. We obtain its electronic structure and absorption spectrum in less than a day of computation time.

show abstract

Adaptive density-guided approach to double incremental potential energy surface construction

Cited by 11 publications

References 78 publications

Vibrational Coupled Cluster Computations in Polyspherical Coordinates with the Exact Analytical Kinetic Energy Operator

Vibrational Coupled Cluster Computations in Polyspherical Coordinates with the Exact Analytical Kinetic Energy Operator

Quasi-direct Quantum Molecular Dynamics: The Time-Dependent Adaptive Density-Guided Approach for Potential Energy Surface Construction

Massively Parallel Fragment-Based Quantum Chemistry for Large Molecular Systems: The Serestipy Software

Contact Info

Product

Resources

About