A modified self-consistent phonon theory of

hydrogen bond melting

Cite as: J. Chem. Phys. 80, 2242 (1984); https://doi.org/10.1063/1.446921
Submitted: 29 August 1983 . Accepted: 08 November 1983 . Published Online: 31 August 1998

Y. Gao, and E. W. Prohofsky

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© 1984 American Institute of Physics.

A modified self-consistent phonon theory of hydrogen bond melting
Y. Gao and E. W. Prohofsky
Department ofPhysics, Purdue University, West Lafayette, Indiana 47907

(Received 29 August 1983; accepted 8 November 1983)

The calculation reported here is the simplest model cal-
culation relevant to particular hydrogen bond meltings
which are important in biological systems. The model shows
general features without the additional complications from
complex structures such as would be the case in DNA helix
melting. The approach uses the self-consistent phonon ap-
proximation (SCPA) which would appear to be a valid ap-
proach in a biological system such as DNA as phonons have
recently been observed to be the form low frequency excita-
tions take. I In particular, a group of optical phonon modes
which stretch the hydrogen bonds in the double helix have
been predicted between 65 and 111 cm - 1.2.3 This seems to be
in agreement with the observation by Raman scattering of a
broad hydrogen bond band centered at 85 cm - 1. 4 This band
has been reported to behave anomalously as the helix melt-
ing temperature is approached.
The SCP A S has been very successful in solid state appli-
cations but fails at temperatures approaching the melting
temperature. The failure arises because simple SCPA does
ammonia positions. In the article it was shown that this po-
tential could be very well approximated by a Morse potential
with particular parameters.
Our lattice calculations were one dimensional assuming
displacements only along the H -bond axis. We solved for the
single vibrational frequency for two point masses, each an
NH3 molecule connected by the self-consistent force con-
stant. This would approximate one dimensional solid am-
monia treated in the Einstein approximation. The potential
is
v = Vol 1 - exp[( - a(r-Ro)] )2 - Vo (1)
with Vo = 3.48 kcaI!mol, Ro = 3.37 A, and a = 1.22 A -I.
D = (Mw)-Icoth(! /3w), where M is the mass of an ammonia
molecule and W determined from !MW2 = r/J.
The equation for r/J in SCPA S •8 •9 reduces in one dimen-
sion to
r/J=
f ( d
2
duexp - U-) -V(RT+U)
2

not properly handle odd terms in an anharmonic potential.

An improved self-consistent approach (ISC) has been devel-
oped which is valid to higher temperatures. 6 In ISC the odd
X [ f
2D du 2

du exp ( - ;;) r I , (2)

terms are treated in a series expansion. In an attempt to over-

where 11 is the displacement from R T and R T is determined
come the limitations of the expansion at large amplitudes we
from the condition that V (R T + 110) is equal to V (R T - 110)'
have modified the SCPA so as to include thermal expansion
where 110 is the half-width of the Gaussian weighting func-
effects directly into the initial SCP A integral which is used in
tion in Eq. (2) which is proportional to D (lf2).
calculating r/Jij the effective force constant. That is, the ther-
The calculated value of R T as a function of temperature
modynamic weighting takes place with a probability distri-
is shown in Fig. 1. The region of rapid increase from a rea-
bution which also includes displacement of the mean posi-
tion. This thermal expansion is also determined
self-consistently. In our calculation four parameters
Dij(WkoT), wdr/Jij)' RT(Dij)' and r/Jij (Dij' R T ) are solved for 12.00
self-consistency where Dij = ( ~ij ~ij) is the displacement
correlation function with the brackets implying a suitable
averaging process and Wk represents the eigenfrequencies 10.
and eigenvectors of the phonon modes using the proper ef-
fective force constants. The temperature enters through the
calculation of D ij which is the correlated motion of i and j at
a particular level of thermal excitation. The force constant cr 8.00
Z
.....
r/Jij is then a thermodynamically weighted best parameter
from the true potential which takes into account the correla- '-:l
.....
tion in motion between atoms. s RT is the thermally expand- 0:: 8.
ed mean position determined by requiring the classical tur-
naround points of the effective oscillator to be at the same
value of the true potential on both sides ofthe potential mini- ".00
mum.
We have chosen for the bare hydrogen bond potential a
model based on ab initio orbital calculations for two hydro- ~004------'r------r------r-----~------'
gen bonded ammonia molecules. 7 The energy is calculated as .0 100.0 '100.0 500.0
a function of nitrogen-nitrogen distance assuming that the
bonding hydrogen is at its equilibrium position for each N- FIG. I. The mean interatomic N-N distance in angstroms as a function of
N distance and that all other hydrogens are at their usual temperature.

2242 J. Chern. Phys. 80 (5). 1 March 1984 0021-9606/84/052242-02$02.10 © 1984 American Institute of Physics
 Letters to the Editor
sonable to unreasonable value is what we associate with
melting. The behavior is of course not strongly cooperative
as would be expected for a three dimensional material in
which all bonds melt.
If we attempt to simulate a 3D solid by simply assuming
that more degrees of freedom exist which will all contribute
to D we can lower the melting temperature to the melting
temperature of solid ammonia. Increasing D by 41r13 which
would account for the extra degrees of freedom works very
well. The factor 1/3 comes from taking the component of
displacement on the bond direction. The one dimensional
case, however, matches the melting temperature of DNA
quite well.
Resonant interactions of normal modes in rotating classical molecules
J. Andrew Combs and William G. Hoover
Department ofApplied Science. University of California at Davis. Davis. California 95616
(Received 31 August 1983; accepted 16 November 1983)
During numerical work on classical energy transfer in
molecules we found that pairs of normal modes in isolated
rotating molecules resonate, i.e., energy is exchanged strong-
ly among modes that have nearly the same frequency. In the
case of a degenerate mode pair, energy initially concentrated
in one mode, is completely transferred into the other mode
after rotating through a characteristic angle
Or = 1T/2~, (1)
where 0 < ~.:;; 1 is a measure of the Coriolis coupling between
the modes. This is found to be true regardless of the magni-
tude of the angular frequency of rotation n, as long as the
atomic displacements from their equilibrium positions re-
main small.
It turns out that, for two modes i andj, ~ = le;j I, where
eij = n·Lxdi)xxd;).
k
nis a unit vector in the direction ofthe angular velocity n,
Xk (i) is the eigenvector of the ith mode associated with the
k th atom and is obtained from the appropriate force con-
stant matrix of the molecule; the sum is taken over all atoms
in the molecule. Coriolis coupling can occur between two
modes, therefore, when the cross product of their respective
eigenvectors summed over the molecule [i.e., Eq. (2)] does
not vanish. This is equivalent to Jahn's rule. I
Analysis reveals that Newton's equations of motion in
the harmonic approximation admit coupled normal vibra-
tions when the Coriolis and centrifugal terms are fully re-
tained, aslongasn~nJi, where both no andnare constant.
Degenerate normal modes couple strongly through the Cor-
iolis term. Consider, e.g., a pair of in-plane degenerate modes
(call them 1 and 2) vibrating at the frequency W in a planar
molecule rotating such that n is perpendicular to the molec-
ular plane. For the particular case where the energy is initial-
J. Chern. Phys. 80 (5). 1 March 1984 0021-9606/84/052243-02$02.10
This work was supported in part by a grant from In-
diana Elks Cancer Research.
1H. Urabe, Y. Tominaga. and K. Kubota. J. Chem. Phys.78, 5937 (1983).
lE. W. Prohofsky. K. C. Lu, L. L. Van Zandt, and B. F. Putman, Phys. Lett.
A 70, 492 (1979).
3E. W. Prohofsky (in press).
4H. Urabe and Y. Tominaga, J. Phys. Soc. Jpn. 50, 3543 (1981).
'N. R. Werthamer, Am. J. Phys. 37. 763 (1969).
6V. V. Goldman, G. K. Horton, and M. L. Klein, Phys. Rev. Lett. 21, 1527
(1968).
7N. C. Baird, Int. J. Quantum Chem. Symp. 1,49 (1974).
8L. H. Nasanow, Phys. Rev. 146. 120 (1966).
"P. F. Choquard. The Anharmonic Crystal (W. A. Benjamin. New York,
1967).
ly concentrated entirely in mode 1 the energies El and E2 of
the two modes become
El =A cos2 ~e(t) + 0 (~o ).
(3)
E2=Asin2~e(t)+O(~0). (4)
where A is a constant and e = not is the angle through
which the molecule has rotated after time t; the higher order
terms oscillate with a frequency slightly shifted from w.
Thus, all the energy is initially concentrated in mode 1 and
transfers to mode 2 after the molecule rotates through an
angle e = en where e r is defined by Eq. (1). The rate of
transition is proportional to ~no. It also is true that the sum
El + E2 is a constant, except for a correction of the order
n ~/W2. These conclusions are valid no matter how small no
(2)
becomes, as long as no is not zero.
The in-plane nondegenerate modes couple also, but
much more weakly than do the degenerate modes. It can be
shown that the mode energy oscillates with an amplitude of
the order n ~~ 2WIW2/(wf - W~ )2, for those modes which sa-
tisfy the inequality
8n~~2(wi +w~)I(wf -w~f<l,
where WI and W2 are the frequencies of modes 1 and 2. Thus,
as the ratio n ~~ 2WIW2 /(wf - w~ f is decreased nondegener-
ate modes rapidly decouple and the resonance phenomenon
disappears.
For molecular rotations oriented at arbitrary angles
with respect to the molecular plane, centrifugal couplings
and distortions are introduced; however, these effects only
cause bond stretching and minor frequency shifts in addition
to those encountered in their absence. If; is allowed to van-
ish, the centrifugal coupling of degenerate modes merely lifts
the degeneracy since a new linearly independent combina-
@ 1984 American Institute of PhysiCS 2243