Analytic G0W0 gradients based on a double-similarity transformation equation-of-motion coupled-cluster treatment

Area of Science:

• Quantum chemistry
• Computational physics
• Theoretical chemistry

Background:

• Accurate prediction of ionization potentials (IPs) is vital for understanding molecular properties like reactivity and spectroscopy.
• Calculating adiabatic IPs is computationally challenging due to the need for nuclear gradients of ionized states within correlated electronic structure methods.

Purpose of the Study:

• To present a novel, fully analytic formulation for calculating GW (Green's function) nuclear gradients.
• To address limitations in traditional coupled-cluster doubles (CCD) methods by incorporating missing correlation effects.

Main Methods:

• Development of analytic GW nuclear gradients based on a modified equation-of-motion coupled-cluster doubles (EOM-CCD) formalism.
• Leveraging formal connections between GW theory and CCD methods.

Main Results:

• A fully analytic formulation for GW nuclear gradients has been derived.
• The new method enables the inclusion of correlation effects often missing in standard CCD approaches.

Conclusions:

• The presented analytic GW gradient formulation offers a more accurate and efficient method for computing adiabatic ionization potentials.
• This advancement is applicable to both finite and extended systems, broadening its utility in computational chemistry and physics.