isomer selection in no 2 ˉ · h 2 o · ar rachael relph rob roscioli, ben elliott, joe bopp, tim...

Isomer Selection inNO2ˉ · H2O · Ar

Rachael RelphRob Roscioli, Ben Elliott,

Joe Bopp, Tim Guasco, George GardenierMark Johnson

Johnson LabYale University

Presented at63rd International Symposium on Molecular Spectroscopy

The Ohio State University

This project was made possible by:

Pre

diss

ocia

tion

Yie

ld

1000 1400 1800 2800 3200 3600

Photon Energy, cm-1

The NO2‾ · H2O SystemNO2ˉ · H2O · Ar + h → NO2ˉ · H2O + Ar

Pre

diss

ocia

tion

Yie

ld

Photon Energy, cm-1

OH Stretching Region

2800 3000 3200 3400 3600 3800

Clˉ · H2O

NO2ˉ · H2O

IHB

free

MS-IR-MS-IR-MS

Sig

na

lTime of Flight, s

Argon-solvated Isomer 1Argon-solvated Isomer 2Isomer 2 fragment induced by pump laserIsomer 2 fragment induced by probe laser

hpump (P1)(scanned)

hprobe (P2)(fixed)

po

pu

latio

n

Reflectron 1 (R1)

Reflectron 2(R2)

Coaxial TOF(PA)

po

pu

latio

n

±1.5 keV

probefragment

pumpfragment

probefragment

pumpfragment

MS-IR-MS-IR-MS

Sig

na

lTime of Flight, s

Argon-solvated Isomer 1Argon-solvated Isomer 2Isomer 2 fragment induced by pump laserIsomer 2 fragment induced by probe laser

hpump (P1)(scanned)

hprobe (P2)(fixed)

po

pu

latio

n

Reflectron 1 (R1)

Reflectron 2(R2)

Coaxial TOF(PA)

po

pu

latio

n

±1.5 keV

2800 3000 3200 3400 3600 3800

Ion

Dip

Sig

nal

Pre

diss

ocia

tion

Yie

ld

Photon Energy, cm-1

Ion

Dip

Sig

nal

A

B

Sig

na

lTime of Flight, s

Argon-solvated Isomer 1Argon-solvated Isomer 2Isomer 2 fragment induced by pump laserIsomer 2 fragment induced by probe laser

hpump (P1)(scanned)

hprobe (P2)(fixed)

po

pu

latio

n

Reflectron 1 (R1)

Reflectron 2(R2)

Coaxial TOF(PA)

po

pu

latio

n

±1.5 keV

Motions of the Water Molecule

2800 3000 3200 3400 3600 3800

Ion

Dip

Sig

nal

Pre

diss

ocia

tion

Yie

ld

Photon Energy, cm-1

Ion

Dip

Sig

nal

A

B

Motions of the Water Molecule

Solvation Effects on NO2‾

Sig

na

lTime of Flight, s

Argon-solvated Isomer 1Argon-solvated Isomer 2Isomer 2 fragment induced by pump laserIsomer 2 fragment induced by probe laser

hpump (P1)(fixed)

hprobe (P2)(fixed)

po

pu

latio

n

Reflectron 1 (R1)

Reflectron 2(R2)

Coaxial TOF(PA)

po

pu

latio

n

±1.5 keV

Time of Flight, s

1000 1100 1200 1300 1400 1500

Photon Energy, cm-1

Time of Flight, s

Time of Flight, s

pump B

pump A

pump B

pump A

probefragment

modulation

probefragment

modulation

Pre

diss

ocia

tion

Yie

ld

NO str (back)2

Solvation Effects on NO2‾

2800 3000 3200 3400 3600 3800P

redi

ssoc

iatio

n Y

ield

Photon Energy, cm-1

AB

1000 1100 1200 1300 1400 1500

Photon Energy, cm-1

Time of Flight, s

Time of Flight, s

pump B

pump A

pump B

pump A

probefragment

modulation

probefragment

modulation

Pre

diss

ocia

tion

Yie

ld

1000 1400 1800 2800 3200 3600

Pre

diss

oci

atio

n Y

ield

Photon Energy, cm-1

Conclusions

Successful application to a system with non-trivial spectral overlap of isomers

Demonstration of single point averaging approach to extend spectral range

Elucidation of solute response to different hydration motifs

Good prospects for providing secure assignments in many unpublished examples

of complex hydrated ion spectra

1000 1400 1800 2800 3200 3600

Ca

lcu

late

d I

nte

nsi

tyP

red

isso

cia

tion

Yie

ld

Photon Energy, cm-1

The NO2‾ · H2O SystemNO2ˉ · H2O · Ar + h → NO2ˉ · H2O + Ar