The role of higher CO-multipole moments in understanding the dynamics of photodissociated carbonmonoxide in myoglobin.

Abstract:

:The influence of electrostatic multipole moments up to hexadecapole on the dynamics of photodissociated carbon monoxide (CO) in myoglobin is investigated. The CO electrostatic potential is expressed as an expansion into atomic multipole moments of increasing order up to octopole which are obtained from a distributed multipole analysis. Three models with increasingly accurate molecular multipoles (accurate quadrupole, octopole, and hexadecapole moments, respectively) are developed and used in molecular dynamics simulations. All models with a fluctuating quadrupole moment correctly describe the location of the B-state whereas the sign of the octopole moment differentiates between the Fe...CO and Fe...OC orientation. For the infrared spectrum of photodissociated CO, considerable differences between the three electrostatic models are found. The most detailed electrostatic model correctly reproduces the splitting, shift, and width of the CO spectrum in the B-state. From an analysis of the trajectories, the spectroscopic B(1) and B(2) states are assigned to the Fe...CO and Fe...OC substates, respectively.

journal_name

Biophys J

journal_title

Biophysical journal

authors

Plattner N,Meuwly M

doi

10.1529/biophysj.107.120519

subject

Has Abstract

pub_date

2008-04-01 00:00:00

pages

2505-15

issue

7

eissn

0006-3495

issn

1542-0086

pii

S0006-3495(08)70506-X

journal_volume

94

pub_type

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