Department of Chemistry

Recent advances in quantum information and quantum science have inspired the development of various compact, dynamically structured ansätze that are expected to be realizable in Noisy Intermediate-Scale Quantum (NISQ) devices. However, such ansätze construction strategies hitherto developed involve considerable measurements, and thus, they deviate significantly in the NISQ platform from their ideal structures. Therefore, it is imperative that the usage of quantum resources be minimized while retaining the expressivity and dynamical structure of the ansatz that can adapt itself depending on the degree of correlation. We propose a novel ansatz construction strategy based on the ab initio many-body perturbation theory that requires no pre-circuit measurement and, thus, remains structurally unaffected by any hardware noise. The accuracy and quantum complexity associated with the ansatz are solely dictated by a pre-defined perturbative order, as desired, and, hence, are tunable. Furthermore, the underlying perturbative structure of the ansatz construction pipeline enables us to decompose any high-rank excitation that appears in higher perturbative orders into the product of various low-rank operators, and it thus keeps the execution gate-depth to its minimum. With a number of challenging applications on strongly correlated systems, we demonstrate that our ansatz performs significantly better, both in terms of accuracy, parameter count, and circuit depth, in comparison to the allied unitary coupled cluster based ansätze.

Herein we report on the investigation of microwave-assisted catalytic transfer hydrogenation (TH) of carbonyl and nitro compounds by employing Ru(II) complexes bimetallic [(p-cymene)2(RuCl)2L1]2X (X = BF4(Cat2); X = PF6(Cat3)) and mononuclear [(p-cymene)(RuCl)L2]BF4(Cat4) (where L1= N,N'-(3,3',5,5'-tetraisopropyl-[1,1'-biphenyl]-4,4'-diyl)bis(1-(pyridin-2-yl)methanimine); L2 = N-(2,6-diisopropyl-phenyl)-1-(pyridin-2-yl)-methanimine). At a low catalyst loading of 0.01 mol% (Cat2/Cat3), a broad substrate scope has been achieved for aromatic as well as aliphatic ketones and aldehydes, with a short reaction time of just 10 minutes. Additionally, chemoselective hydrogenation of nitroaromatic compounds has been achieved under microwave irradiation by Cat2 within 5 minutes. Control experiments demonstrate that microwave heating conditions outperform conventional heating method in terms of improved catalytic activity and reaction efficiency. The bimetallic Cat2 catalyst can be used at a very low loading of 0.001 mol% to achieve the high TONs and TOFs of 7.7 × 104and 2.3 × 105h-1, respectively, for TH reaction. Spectrometry experiments for intermediate trapping have been used to propose a probable mechanism for TH of carbonyl compounds.

Conical intersection (CI) leads to fast electronic energy transfer. However, Hamm and Stock [Phys. Rev. Lett. 109, 173201 (2012)] showed the existence of a vibrational CI and its role in vibrational energy relaxation. In this paper, we further investigate the vibrational energy relaxation using an isolated model Hamiltonian system of four vibrational modes with two distinctively different timescales (two fast modes and two slow modes). We show that the excitation of the slow modes plays a crucial role in the energy relaxation mechanism. We also analyze the system from a mixed quantum-classical (surface hopping method) and a completely classical point of view. Notably, surface hopping and even classical simulations also capture fast energy relaxation, which is a signature of CI’s existence.