Efficient Semi-numerical Implementation of Global and Local Hybrid Functionals for Time-Dependent Density Functional...

Area of Science:

• Computational Chemistry
• Quantum Chemistry
• Theoretical Chemistry

Background:

• Local hybrid functionals provide greater flexibility than global hybrids.
• This flexibility is anticipated to benefit calculations of electronic excitations using time-dependent density functional theory (TDDFT).

Purpose of the Study:

• To report the first linear-response TDDFT implementation of local hybrid functionals using a semi-numerical integration technique.
• To evaluate the efficiency and accuracy of this new implementation.

Main Methods:

• A semi-numerical integration technique was employed for the linear-response TDDFT implementation of local hybrid functionals.
• The performance was assessed by comparing timings and accuracy against analytical methods for time-dependent Hartree-Fock (TDHF) and the TPSSh global hybrid.
• The Resolution of Identity (RI) approximation was used for the Coulomb part of the kernel.

Main Results:

• The semi-numerical implementation is faster than existing analytical methods for global hybrid functionals in the TURBOMOLE code, even for small systems.
• Timings for global and local hybrids are comparable with the semi-numerical approach.
• The new method facilitates TDDFT calculations with local hybrid functionals for large systems.

Conclusions:

• The development of a semi-numerical linear-response TDDFT implementation of local hybrid functionals opens new possibilities for computational chemistry.
• This approach enables efficient calculations for larger systems, paving the way for evaluating more sophisticated local hybrid functional parametrizations.