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arXiv:1409.0784

Selective Vibrational Population Transfer using Combined STIRAP and Counter-Diabatic Fields

Shumpei Masuda, Stuart A. Rice

Published Sep 2, 2014• 2 citations
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Abstract

We report studies of state-to-state vibrational energy transfer in an isolated polyatomic molecule driven by combined stimulated Raman adiabatic passage (STIRAP) and counter-diabatic fields (CDF), using as vehicles selective population of one of a pair of near degenerate states in SCCl$_2$ and enhancing the yield of HNC in the HCN/HNC isomerization reaction. The efficiency of the population transfer within a subset of states embedded in a dense manifold of states is examined for the cases that the transition dipole moments between the initial and target states are much smaller than and comparable to the transition dipole moments between background states, and for the case that the subset states have large transition dipole moments with the background states. We show that, in a subset of states that is coupled to background states, a combination of STIRAP fields and CDFs that do not individually generate processes that are competitive with the desired population transfer can generate greater population transfer efficiency than can ordinary STIRAP with field strength and/or pulse duration similarly restricted. We also show that the exact CDF for an isolated three level system is a useful approximation to the exact CDF for three and five state systems embedded in background states, and we report a study of the stability of the STIRAP + approximate CDF control protocol to variation of the CDF.

DOI
10.48550/arxiv.1409.0784

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We report studies of state-to-state vibrational energy transfer in an isolated polyatomic molecule driven by combined stimulated Raman adiabatic passage (STIRAP) and counter-diabatic fields (CDF), using as vehicles selective population of one of a pair of near degenerate states in SCCl2_22​ and enhancing the yield of HNC in the HCN/HNC isomerization reaction. The efficiency of the population transfer within a subset of states embedded in a dense manifold of states is examined for the cases that the transition dipole moments between the initial and target states are much smaller than and comparable to the transition dipole moments between background states, and for the case that the subset states have large transition dipole moments with the background states. We show that, in a subset of states that is coupled to background states, a combination of STIRAP fields and CDFs that do not individually generate processes that are competitive with the desired population transfer can generate greater population transfer efficiency than can ordinary STIRAP with field strength and/or pulse duration similarly restricted. We also show that the exact CDF for an isolated three level system is a useful approximation to the exact CDF for three and five state systems embedded in background states, and we report a study of the stability of the STIRAP + approximate CDF control protocol to variation of the CDF.
We report studies of state-to-state vibrational energy transfer in an isolated polyatomic molecule driven by combined stimulated Raman adiabatic passage (STIRAP) and counter-diabatic fields (CDFs). The goal of these studies is development of a method for improving the efficiency of level-to-level population transfer under conditions that degrade the efficiency of conventional STIRAP-generated population transfer. The vehicles for our studies are selective population of one of a pair of near-degenerate states in nonrotating SCCl 2 and enhancing the yield of nonrotating HNC in the HCN → HNC isomerization reaction. The efficiency of the population transfer within a subset of states embedded in a manifold of states is examined for the cases in which the transition dipole moments between the initial and target states are much smaller than and comparable to the transition dipole moments between background states and for the case in which the subset states have large transition dipole moments with the background states. We show that, in a subset of states that is coupled to background states, a combination of STIRAP fields and CDFs that do not individually generate processes that are competitive with the desired population transfer can generate population transfer efficiency greater than can ordinary STIRAP with field strength and/or pulse duration similarly restricted and that the exact CDF for an isolated three-level system is a useful approximation to the exact CDF for three- and five-state systems embedded in background states. We report a study of the stability of the STIRAP and approximate CDF control protocol to variation of the CDF intensity, the relative phase between the STIRAP and CDFs, and the pulse duration.
We consider combined stimulated Raman adiabatic passage (STIRAP) and fast-forward field (FFF) control of selective vibrational population transfer in a polyatomic molecule. The motivation for using this combination control scheme is 2-fold: (i) to overcome transfer inefficiency that occurs when the STIRAP fields and pulse durations must be restricted to avoid excitation of population transfers that compete with the targeted transfer and (ii) to overcome transfer inefficiency resulting from embedding of the actively driven subset of states in a large manifold of states. We show that, in a subset of states that is coupled to background states, a combination of STIRAP and FFFs that do not individually generate processes that are competitive with the desired population transfer can generate greater population transfer efficiency than can ordinary STIRAP with similar field strength and/or pulse duration.
Previous studies have demonstrated that when experimental conditions generate non-adiabatic dynamics that prevents highly efficient population transfer between states of an isolated system by stimulated Raman adiabatic passage (STIRAP), the addition of an auxiliary counter-diabatic field (CDF) can restore most or all of that efficiency. This paper examines whether that strategy is also successful in a non-isolated system in which the energies of the states fluctuate, e.g., when a solute is subject to collisions with solvent. We study population transfer in two model systems: (i) the three-state system used by Demirplak and Rice [J. Chem. Phys. 116, 8028 (2002)] and (ii) a four-state system, derived from the simulation studies of Demirplak and Rice [J. Chem. Phys. 125, 194517 (2006)], that mimics HCl in liquid Ar. Simulation studies of the vibrational manifold of HCl in dense fluid Ar show that the collision induced vibrational energy level fluctuations have asymmetric distributions. Representations of these asymmetric energy level fluctuation distributions are used in both models (i) and (ii). We identify three sources of degradation of the efficiency of STIRAP generated selective population transfer in model (ii): too small pulse areas of the laser fields, unwanted interference arising from use of strong fields, and the vibrational detuning. For both models (i) and (ii), our examination of the efficiency of STIRAP + CDF population transfer under the influence of the asymmetric distribution of the vibrational energy fluctuations shows that there is a range of field strengths and pulse durations under which STIRAP + CDF control of population transfer has greater efficiency than does STIRAP generated population transfer.
In the past two decades many schemes to actively control the dynamical evolution of a quantum system have been proposed and established. We focus attention on the use of assisted adiabatic processes to generate selected target states with high efficiency. Specific control protocols that fall in this category are sometimes called shortcuts to adiabaticity. We review two assisted adiabatic population transfer schemes, the counter-diabatic and fast-forward protocols, with the intent of calling attention to their conceptual basis and applications to real systems, specifically vibrational energy transfer in polyatomic molecules and manipulation of Bose-Einstein (BEC) condensates. The particular applications of the counter-diabatic and fast-forward protocols to improving the efficiency of population transfer between vibrational states of a polyatomic molecule that we have studied are (i) selective vibrational energy transfer in the nonrotating thiophosgene (SCCl2) molecule and (ii) enhancing the yield of HNC in the driven rotation free isomerization reaction HCN→CNH. A major component of our considerations concerns reduction of the degradation of population transfer efficiency within a subset of states that is generated by coupling of the subset of states to a manifold of background states. We have examined the influence of a manifold of background vibrational states on population transfer within a subset of embedded vibrational states, and on how that influence can be suppressed. We emphasize that any control protocol must be designed to minimize interference between the background states and excitations within the selected subset of states that are used to define initial and target states. We have also examined the application of the fast-forward protocol to the transport of population between sites of a BEC in an optical lattice. Through the applications we illustrate how the theoretical framework of an assisted adiabatic process depends on the character of the system studied, on the available control parameters, on the constraints imposed by the experimental setting, on the efficiency of population transfer (fidelity) to be achieved, and on the stability of the control process with respect to the variation of the external control fields.
This paper presents a systematic numerical investigation of background state participation in STIRAP (stimulated Raman-adiabatic passage) population transfer among vibrational states, focusing on the consequences for the robustness of the method. The simulations, which are performed over extended grids in the parameter space of the Stokes- and pump pulses (frequencies, field strengths, and pulse lengths), involve hierarchies of (3 + N)-level systems of increasing complexity, ranging from the standard three-level STIRAP setup, (N = 0) in Λ-configuration, up to N = 446. A strongly coupled three-level core system is selected from the full Hamiltonian of the double-well HCN∕HNC system, and the couplings connecting this core system to the remaining states are (re-) parameterized in different ways, from very weak to very strong. The systems so obtained represent a three-level system embedded in various ways in webs of cross-linked vibrational background states and incorporate typical molecular properties. We first summarize essential properties of population transfer in the standard three-level system and quantify the robustness of the method and its dependence on the pulse parameters. Against these reference results, we present results obtained for four (3 + 446)-level systems and several subsystems. For pulse lengths of at most few picoseconds the intrinsic robustness of STIRAP with respect to variations in the field strength disappears as soon as the largest core-background couplings exceed about one tenth of the STIRAP couplings. In such cases robustness with respect to variations in the field strength is entirely lost, since at higher field strengths, except for irregularly spaced narrow frequency ranges, transfer probabilities are strongly reduced. STIRAP-like population transfer is maintained, with some restrictions, at low field strengths near the onset of adiabatic transfer. The suppression of STIRAP is traced back to different mechanisms based on a plentitude of single- and multiphoton transitions to background states, which at the high field strengths characteristic for STIRAP proceed readily even along weakly coupled pathways.
We use a 28-level system consisting of the vibrational bend states of the HCN/HNC system as a model system for the investigation of population transfer across the isomerization barrier using counterintuitively ordered multiphoton (MP) laser pulses. This (m+n)-STIRAP (stimulated Raman-adiabatic passage) arrangement with m pump- and n Stokes-photons is found to be capable of driving HCN→HNC transition states selectively and in a robust manner, despite the presence of near-degenerate parallel processes of different photonicities. Employing Gaussian pulses with widths of 80 ps, the process of highest photonicity we demonstrate is (4+6)-STIRAP, and we investigate systematically the robustness against variations in pulse amplitudes and frequencies for all parallel processes with m=2 and 3, and n=1–6. We discuss the conditions under which selective population transfer is obtained. We also compare with (1+1)-STIRAP using overtone transitions to drive the same state-specific processes and conclude that the few-step sequential MP-STIRAP isomerization is a feasible alternative to the sequential (1+1)-STIRAP based method proposed by Kurkal and Rice [J. Phys. Chem. B 105, 6488 (2001)].