Abstract <p>Vibrational dynamics of the isotopically substituted ozone molecule <InlineEquation ID="IEq7"> <EquationSource Format="TEX">$^{18}$</EquationSource> <EquationSource Format="MATHML"><math> <mmultiscripts> <mrow /> <mrow /> <mn>18</mn> </mmultiscripts> </math></EquationSource> </InlineEquation>O<InlineEquation ID="IEq8"> <EquationSource Format="TEX">$^{16}$</EquationSource> <EquationSource Format="MATHML"><math> <mmultiscripts> <mrow /> <mrow /> <mn>16</mn> </mmultiscripts> </math></EquationSource> </InlineEquation>O<InlineEquation ID="IEq9"> <EquationSource Format="TEX">$^{16}$</EquationSource> <EquationSource Format="MATHML"><math> <mmultiscripts> <mrow /> <mrow /> <mn>16</mn> </mmultiscripts> </math></EquationSource> </InlineEquation>O has been mapped using simple Gaussian IR pulses. The temporal profile of the appropriately positioned vibrational wave packets are examined for use of simple Gaussian UV pulses of suitable width and frequency such that Franck–Condon transport of these vibrational wave packets is routed into the desired dissociation channel on the upper repulsive surface. This careful dovetailing of IR + UV pulses is shown to selectively dissociate the desired bond with considerable yield and branching ratios as high as (<InlineEquation ID="IEq10"> <EquationSource Format="TEX">$^{18}$</EquationSource> <EquationSource Format="MATHML"><math> <mmultiscripts> <mrow /> <mrow /> <mn>18</mn> </mmultiscripts> </math></EquationSource> </InlineEquation>O + <InlineEquation ID="IEq11"> <EquationSource Format="TEX">$^{16}$</EquationSource> <EquationSource Format="MATHML"><math> <mmultiscripts> <mrow /> <mrow /> <mn>16</mn> </mmultiscripts> </math></EquationSource> </InlineEquation>O–<InlineEquation ID="IEq12"> <EquationSource Format="TEX">$^{16}$</EquationSource> <EquationSource Format="MATHML"><math> <mmultiscripts> <mrow /> <mrow /> <mn>16</mn> </mmultiscripts> </math></EquationSource> </InlineEquation>O)/(<InlineEquation ID="IEq13"> <EquationSource Format="TEX">$^{18}$</EquationSource> <EquationSource Format="MATHML"><math> <mmultiscripts> <mrow /> <mrow /> <mn>18</mn> </mmultiscripts> </math></EquationSource> </InlineEquation>O–<InlineEquation ID="IEq14"> <EquationSource Format="TEX">$^{16}$</EquationSource> <EquationSource Format="MATHML"><math> <mmultiscripts> <mrow /> <mrow /> <mn>16</mn> </mmultiscripts> </math></EquationSource> </InlineEquation>O + <InlineEquation ID="IEq15"> <EquationSource Format="TEX">$^{16}$</EquationSource> <EquationSource Format="MATHML"><math> <mmultiscripts> <mrow /> <mrow /> <mn>16</mn> </mmultiscripts> </math></EquationSource> </InlineEquation>O) = 33.6 for 15 fs UV pulse and 171.1 for 10 fs UV pulse. Similarly, the branching ratio (<InlineEquation ID="IEq16"> <EquationSource Format="TEX">$^{18}$</EquationSource> <EquationSource Format="MATHML"><math> <mmultiscripts> <mrow /> <mrow /> <mn>18</mn> </mmultiscripts> </math></EquationSource> </InlineEquation>O–<InlineEquation ID="IEq17"> <EquationSource Format="TEX">$^{16}$</EquationSource> <EquationSource Format="MATHML"><math> <mmultiscripts> <mrow /> <mrow /> <mn>16</mn> </mmultiscripts> </math></EquationSource> </InlineEquation>O + <InlineEquation ID="IEq18"> <EquationSource Format="TEX">$^{16}$</EquationSource> <EquationSource Format="MATHML"><math> <mmultiscripts> <mrow /> <mrow /> <mn>16</mn> </mmultiscripts> </math></EquationSource> </InlineEquation>O)/(<InlineEquation ID="IEq19"> <EquationSource Format="TEX">$^{18}$</EquationSource> <EquationSource Format="MATHML"><math> <mmultiscripts> <mrow /> <mrow /> <mn>18</mn> </mmultiscripts> </math></EquationSource> </InlineEquation>O + <InlineEquation ID="IEq20"> <EquationSource Format="TEX">$^{16}$</EquationSource> <EquationSource Format="MATHML"><math> <mmultiscripts> <mrow /> <mrow /> <mn>16</mn> </mmultiscripts> </math></EquationSource> </InlineEquation>O–<InlineEquation ID="IEq21"> <EquationSource Format="TEX">$^{16}$</EquationSource> <EquationSource Format="MATHML"><math> <mmultiscripts> <mrow /> <mrow /> <mn>16</mn> </mmultiscripts> </math></EquationSource> </InlineEquation>O) increases from 26.3 for 15 fs UV pulse to 60.1 for 10 fs UV pulse. Narrowing of UV pulse width is seen to increase selectivity only with a slight decrease in total yield. The scheme outlined here provides an effective prescription for overcoming the innate internal vibrational relaxation (IVR) built into this illustrative system.</p> Graphical abstract <p></p>

Improved control of selective bond dissociation in isotopically substituted ozone molecule $^{18}$O$^{16}$O$^{16}$O using simple Gaussian IR + UV pulses as an illustrative prescription for overcoming IVR

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2026年6月17日

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Bhavesh K Shandilya,
Manabendra Sarma,
S Adhikari,
Manoj K Mishra

摘要

Abstract

Vibrational dynamics of the isotopically substituted ozone molecule $^{18}$ $^{18}$ O $^{16}$ $^{16}$ O $^{16}$ $^{16}$ O has been mapped using simple Gaussian IR pulses. The temporal profile of the appropriately positioned vibrational wave packets are examined for use of simple Gaussian UV pulses of suitable width and frequency such that Franck–Condon transport of these vibrational wave packets is routed into the desired dissociation channel on the upper repulsive surface. This careful dovetailing of IR + UV pulses is shown to selectively dissociate the desired bond with considerable yield and branching ratios as high as ( $^{18}$ $^{18}$ O + $^{16}$ $^{16}$ O– $^{16}$ $^{16}$ O)/( $^{18}$ $^{18}$ O– $^{16}$ $^{16}$ O + $^{16}$ $^{16}$ O) = 33.6 for 15 fs UV pulse and 171.1 for 10 fs UV pulse. Similarly, the branching ratio ( $^{18}$ $^{18}$ O– $^{16}$ $^{16}$ O + $^{16}$ $^{16}$ O)/( $^{18}$ $^{18}$ O + $^{16}$ $^{16}$ O– $^{16}$ $^{16}$ O) increases from 26.3 for 15 fs UV pulse to 60.1 for 10 fs UV pulse. Narrowing of UV pulse width is seen to increase selectivity only with a slight decrease in total yield. The scheme outlined here provides an effective prescription for overcoming the innate internal vibrational relaxation (IVR) built into this illustrative system.

Graphical abstract

Improved control of selective bond dissociation in isotopically substituted ozone molecule \(^{18}\)O\(^{16}\)O\(^{16}\)O using simple Gaussian IR + UV pulses as an illustrative prescription for overcoming IVR

摘要