Biomedical subjects

Kopin Liu

Publications and source records attributed to Kopin Liu.

At least 19 recordsLinked to original sources

PubMed2006

Product pair correlation in bimolecular reactions.

The vast majority of chemical reactions involve polyatomic species as reactants and/or products. The added degree of complexity offers opportunities to address dynamical questions other than those already encountered in a typical atom + diatom reaction. Product pair correlation is one of them. This article introduces the basic concept, outlines the experimental approach we developed and then highlights some of the applications to bimolecular reaction dynamics. Particular emphasis is placed on the information contents and unique insights gained from this type of measurements, which otherwise would have been lost by the conventional approach.

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PubMed2006

Disentangling mode-specific reaction dynamics from overlapped images.

The hydrogen abstraction reaction between atomic chlorine and C-H stretch-excited CHD(3) was studied under crossed-beam conditions. Prior to collisions, an infrared (IR) laser was used to pump up a fraction of CHD(3) to nu(1) = 1. A time-sliced velocity imaging technique was exploited to image the recoil velocity distribution of the state-selected product CD(3)(nu = 0). For energetic reasons, the IR-on image shows severely overlapped features arising from both the excited and the un-pumped ground-state reagents. A novel threshold method was then developed to directly determine the fraction of IR-excited CHD(3) reagents, which in turn enables us to disentangle the state-selected dynamics from the overlapped images. The results reveal significant differences from previous experimental reports.

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PubMed2006

Recent advances in crossed-beam studies of bimolecular reactions.

A critical overview of the recent progress in crossed-beam reactive scattering is presented. This review is not intended to be an exhaustive nor a comprehensive one, but rather a critical assessment of what we have been learning about bimolecular reaction dynamics using crossed molecular beams since year 2000. Particular emphasis is placed on the information content encoded in the product angular distribution-the trait of a typical molecular beam scattering experiment-and how the information can help in answering fundamental questions about chemical reactivity. We will start with simple reactions by highlighting a few benchmark three-atom reactions, and then move on progressively to the more complex chemical systems and with more sophisticated types of measurements. Understanding what cause the experimental observations is more than computationally simulating the results. The give and take between experiment and theory in unraveling the physical picture of the underlying dynamics is illustrated throughout this review.

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PubMed2006

A crossed-beam study of the F+HD-->HF+D reaction: the resonance-mediated channel.

This is the last report of our extensive studies on the title reaction. Presented here are the state-to-state differential cross section determinations at 11 collision energies, ranging from 1.30 to 4.53 kcal/mol. Together with previously reported results at six lower energies (0.4-1.18 kcal/mol), this perhaps represents one of the most comprehensive set of data from a single investigation for any chemical reaction. The information contents of this set of data are examined in detail, from which the dynamical consequences of reactive resonances are elucidated. Qualitative interpretations of some of the major findings are proposed. Observations that need further theoretical investigations for better physical understanding are pointed out.

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PubMed2006

A crossed-beam study of the F+HD-->DF+H reaction: the direct scattering channel.

State-to-state differential cross sections of the title reaction are presented at four collision energies, ranging from 1.18 to 4.0 kcal /mol. Product angular distributions are predominantly backscattered at low energies and shift toward sideways (peaking near 150 degrees ) at higher energies. Experimental evidence for contributions from migratory trajectories was found in the more detailed angle-specific internal state distributions. The dynamics of this reaction is mostly governed by classical mechanics, and several major findings can qualitatively be rationalized. These "classical" behaviors serve as "references" and are to be contrasted to the attributes observed for the other isotopic product channel, HF+D, in a forthcoming paper.

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PubMed2006

State-correlation matrix of the product pair from F + CD(4)--> DF(nu') + CD(3)(0 v(2) 0 0).

The title reaction was investigated under crossed-beam conditions at three different collision energies, E(c) = 8.4, 2.76 and 1.46 kcal mol(-1). The combination of using a (2 + 1) resonance-enhanced multiphoton ionization for tagging state-specific CD(3) products and exploiting a time-sliced velocity imaging for ion detection allows us to reveal the coincident information of the two product pairs in a state-correlated manner. The pair-correlated results are reported for the two product vibrators -- (v(2) = 0, v'), (v(2) = 1, v'), (v(2) = 2, v') and (v(2) = 3, v')-and the dynamics attributes we examined include product state distributions, energy disposals and angular distributions. Together with our earlier communications, a rather complete picture of the correlated dynamics of the title reaction emerges. One of the major findings, the anti-correlated excitations of the two product vibrators at all four energies of this study, can qualitatively be understood by kinematics arguments.

Algorithms↗

PubMed2006

Rotationally selected product pair correlation: F+CD4 --> DF(nu')+CD3(nu2 = 0 and 2, N).

The product pair correlation of the title reaction was measured with rotational selection for both the vibrationally ground CD3(nu = 0) and umbrella-excited CD3(nu2 = 2) products. A striking linear relationship was found between the rotational energy of the selected CD3 product and the correlated kinetic energy release (or the average vibrational energy of the DF coproduct). Such a linearly correlated (or anticorrelated) dependence appears to be stronger for CD3(nu2 = 2,N) than for CD3(nu = 0,N). The mechanistic implication of the observation is that the rotational motion N of the CD3 product tends to lie antiparallel to the orbital angular momentum l' of the two departing products. The dependency on the K quantum number--the projection of N on the top axis--is, on the other hand, less significant yet noticeable.

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PubMed2005

Imaging the reaction dynamics of OH + CD4. 2. Translational energy dependencies.

The reaction of OH + CD4 is investigated in a crossed-beam experiment over the collisional energies ranging from reaction threshold of about 5 to 16 kcal/mol. Exploiting a time-sliced ion velocity imaging detection scheme, the coincident information on the two polyatomic product pairs, HOD and CD3, is revealed in a state-correlated manner. The recently discovered vibrational mode-correlation between the two products is found to persist over the full range of collision energies of this study. In addition, the energy dependencies of the correlated cross section, state distribution, and angular distribution are elucidated, providing an unprecedented insight into this important reaction.

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PubMed2005

Imaging the reaction dynamics of OH + CD4. 3. Isotope effects.

Isotope effects in the reaction of hydroxyl radical with methane are investigated in a crossed-beam experiment. By exploiting different combinations of OH/OD + CH4/CD4/CHD3, a total of eight isotopically variant reactions are examined to decipher the dynamical consequence of both primary and secondary isotope effects. The most prominent observation is from isotopic substitution of the transferred atom (primary isotope effect), which yields more stretch-excited water product for the D atom case than H atom. The opposite is found, however, for excitations in bending and combination modes. The secondary isotope effects, from either substituted hydroxyl radical or the three H atoms that are not being abstracted, are relatively minor and manifest themselves in spreading the vibrational distribution of the water coproducts.

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PubMed2005

How active is the bend excitation of methane in the reaction with O(3P)?

The role of bending excitation of methane in the reaction with O(3P) is investigated in a crossed-beam experiment. Previous theories predicted that either stretch or bend excitation of the reactant promotes chemical reactivity and that initial bending excitation of CH4 preferentially yields umbrella-excited CH3 products. Experimentally, both predictions for bend-excited reagent were not borne out in this investigation. We found instead that compared to the ground-state reagent, bend-excited methane yields more vibrational excitation of the hydroxyl coproduct. The first reported product angular distributions show predominant backward scatterings for both ground-state and bend-excited methanes, which corroborate well with a direct rebound reaction mechanism.

Letter↗

PubMed2005

Mode correlation of product pairs in the reaction OH+CD4-->HOD+CD3.

The hydrogen abstraction reaction from methane by a hydroxyl radical produces two polyatomic molecules. Each product has several vibrational modes that characterize distinct, concerted motions of the constituent atoms of the molecule. This communication describes the first measurement that maps out the coincident information on how the mode of excitation of one product varies with that of the other co-product. Such information on mode correlation of product pairs is particularly appealing in that it provides intuitively a glimpse of the reaction paths by which the chemical transformation occurs.

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PubMed2005

Imaging the "missing" bands in the resonance-enhanced multiphoton ionization detection of methyl radical.

Three small features were uncovered in the (2+1) resonance-enhanced multiphoton ionization spectra of CD(3) produced from a crossed-beam reaction of F+CHD(3) near reaction threshold. Taking the velocity mapped images of these features revealed several well-resolved ringlike structures. By conservation of energy, these spectral features were unambiguously assigned to the "missing" bands of 1(1) (1), 3(1) (1), and 4(1) (1) in the literature. These assignments enable all four modes of excitation of this important radical being detected, which could have significant impact on future dynamics studies of the mode specificity of methyl radical.

Computer Simulation↗

PubMed2005

Imaging a reactive resonance in the Cl+CH(4) reaction.

The title reaction has been under extensive experimental and theoretical investigations. Presented here is the experimental evidence suggesting a reactive resonance in this reaction-an intriguing possibility that has been hitherto unsuspected. The initial speculation was inferred from theoretical works in the literature, and subsequent confirmation came from the observed pattern of the angular distributions of the HCl(nu'=1)+CH(3)(upsilon=0) product pair, when plotted in the angle-collision energy plane. This characteristic pattern proves particularly incisive and universal in revealing the imprint of reactive resonance in experimental observable. The nature of the proposed resonance in this reaction is also elucidated.

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PubMed2005

Imaging the mode-selected predissociation of OCS+[(v1v2v3)B2 Sigma+].

A new experimental approach to explore the mode-selected chemistry is proposed and demonstrated here. In this approach a double-resonance excitation scheme is exploited to prepare a well-defined mode or state of a parent ion. A time-sliced velocity imaging technique interrogates the fragment ion from the subsequent predissociation. Application to the title process reveals remarkable mode-specific behaviors despite the long dissociation time associated with the indirect bond-breaking process. A qualitative interpretation of the major findings is surmised.

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PubMed2004

Observation of a reactive resonance in the integral cross section of a six-atom reaction: F+CHD3.

The title reaction was investigated under crossed-beam conditions at collisional energies ranging from about 0.4 to 7.5 kcal/mol. Product velocity distributions were measured by a time-sliced, velocity-map imaging technique to explicitly account for the density-to-flux transformation factors. Both the state-resolved, pair-correlated excitation functions and vibrational branching ratios are presented for the two isotopic product channels. An intriguing resonance tunneling mechanism occurring near the reaction threshold for the HF+CD3 product channel is surmized, which echoes the reactive resonances found previously for the F+HD-->HF+D reaction and more recently for the F+CH4 reaction.

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PubMed2004

Rotationally selected product pair correlation in F+CD(4)-->DF(nu('))+CD(3)(nu=0,N).

The title reaction was studied in a crossed-beam experiment by imaging of state-selected products. The rotational state selection of the CD(3) products was achieved using (2+1) resonance-enhanced multiphoton ionization. The coincident information on the DF coproducts was revealed in a state-resolved manner from time-sliced velocity map images. Significant dependences of both the correlated differential cross sections and the DF vibrational branching ratios on the "tagged" CD(3) rotation states were found. The dynamical implications of one of the major findings are discussed.

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PubMed2004

Reactive resonance in a polyatomic reaction.

In the course of an extensive investigation aimed at understanding the detailed mechanisms of a prototypical polyatomic reaction, several remarkable observations were uncovered. To interpret these findings, we surmise the existence of a reactive resonance in this polyatomic reaction. The reaction of concern is F+CH4-->HF+CH3, and the abnormal attributes were revealed only near the reaction threshold. The discovery of reactive resonance in a polyatomic reaction is more than just an extension from a typical atom+diatom reaction. As shown here, it holds great promise to disentangle the elusive intramolecular vibrational dynamics of transient collision complex in the critical transition-state region.

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PubMed2004

Imaging the pair-correlated excitation function: The F+CH4-->HF(v')+CH3(nu=0) reaction.

The velocity map ion imaging technique was applied to measure the reaction excitation function for the first time. It was found that the "raw" excitation function was significantly distorted by the density-to-flux transformation of the title reaction. Through a systematic investigation, possible reasons for such a dramatic effect are outlined. In addition, the state-resolved, pair-correlated excitation functions and branching ratios are presented. Effects of imperfect time slicing in the time-sliced velocity imaging technique in general are also discussed.

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