The concept of resonance-assisted hydrogen bonds(RAHBs)highlights the synergistic interplay between theπ-resonance and hydrogen bonding interactions.This concept has been well-accepted in academia and is widely used ...The concept of resonance-assisted hydrogen bonds(RAHBs)highlights the synergistic interplay between theπ-resonance and hydrogen bonding interactions.This concept has been well-accepted in academia and is widely used in practice.However,it has been argued that the seemingly enhanced intramolecular hydrogen bonding(IMHB)in unsaturated compounds may simply be a result of the constraints imposed by theσ-skeleton framework.Thus,it is crucial to estimate the strength of IMHBs.In this work,we used two approaches to probe the resonance effect and estimate the strength of the IMHBs in the two exemplary cases of the enol forms of acetylacetone and o-hydroxyacetophenone.One approach is the block-localized wavefunction(BLW)method,which is a variant of the ab initio valence bond(VB)theory.Using this approach,it is possible to derive the geometries and energetics with resonance shut down.The other approach is Edmiston’s truncated localized molecular orbital(TLMO)technique,which monitors the energy changes by removing the delocalization tails from localized molecular orbitals.The integrated BLW and TLMO studies confirmed that the hydrogen bonding in these two molecules is indeed enhanced byπ-resonance,and that this enhancement is not a result ofσconstraints.展开更多
The incoherent control of finite-level quantum systems is investigated. Following a brief introduction to coherent control paradigms in quantum control, a control problem that can not be accomplished using only cohere...The incoherent control of finite-level quantum systems is investigated. Following a brief introduction to coherent control paradigms in quantum control, a control problem that can not be accomplished using only coherent control is presented. For such a control problem, it is proved that it can be accomplished using incoherent control based on projective measurement and coherent control for two classes of finite-level quantum systems, i.e., eigenstate controllable quantum systems and wavefunction controllable quantum systems.展开更多
文摘The concept of resonance-assisted hydrogen bonds(RAHBs)highlights the synergistic interplay between theπ-resonance and hydrogen bonding interactions.This concept has been well-accepted in academia and is widely used in practice.However,it has been argued that the seemingly enhanced intramolecular hydrogen bonding(IMHB)in unsaturated compounds may simply be a result of the constraints imposed by theσ-skeleton framework.Thus,it is crucial to estimate the strength of IMHBs.In this work,we used two approaches to probe the resonance effect and estimate the strength of the IMHBs in the two exemplary cases of the enol forms of acetylacetone and o-hydroxyacetophenone.One approach is the block-localized wavefunction(BLW)method,which is a variant of the ab initio valence bond(VB)theory.Using this approach,it is possible to derive the geometries and energetics with resonance shut down.The other approach is Edmiston’s truncated localized molecular orbital(TLMO)technique,which monitors the energy changes by removing the delocalization tails from localized molecular orbitals.The integrated BLW and TLMO studies confirmed that the hydrogen bonding in these two molecules is indeed enhanced byπ-resonance,and that this enhancement is not a result ofσconstraints.
基金supported by the National Natural Science Foundation of China(60805029and60703083)the project from the State KeyLaboratory of Industrial Control Technology,Zhejiang University
文摘The incoherent control of finite-level quantum systems is investigated. Following a brief introduction to coherent control paradigms in quantum control, a control problem that can not be accomplished using only coherent control is presented. For such a control problem, it is proved that it can be accomplished using incoherent control based on projective measurement and coherent control for two classes of finite-level quantum systems, i.e., eigenstate controllable quantum systems and wavefunction controllable quantum systems.
