Calculating energy derivatives for quantum chemistry on a quantum computer

Abstract

Abstract Modeling chemical reactions and complicated molecular systems has been proposed as the “killer application” of a future quantum computer. Accurate calculations of derivatives of molecular eigenenergies are essential toward this end, allowing for geometry optimization, transition state searches, predictions of the response to an applied electric or magnetic field, and molecular dynamics simulations. In this work, we survey methods to calculate energy derivatives, and present two new methods: one based on quantum phase estimation, the other on a low-order response approximation. We calculate asymptotic error bounds and approximate computational scalings for the methods presented. Implementing these methods, we perform geometry optimization on an experimental quantum processor, estimating the equilibrium bond length of the dihydrogen molecule to within $$0.014$$ <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mn>0.014</mml:mn></mml:math> Å of the full configuration interaction value. Within the same experiment, we estimate the polarizability of the H $${}_{2}$$ <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:msub><mml:mrow/><mml:mrow><mml:mn>2</mml:mn></mml:mrow></mml:msub></mml:math> molecule, finding agreement at the equilibrium bond length to within $$0.06$$ <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mn>0.06</mml:mn></mml:math> a.u. ( $$2 \%$$ <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:mn>2</mml:mn><mml:mi>%</mml:mi></mml:mrow></mml:math> relative error).