<html><head><meta http-equiv="content-type" content="text/html; charset=UTF-8"><style>body { line-height: 1.5; }blockquote { margin-top: 0px; margin-bottom: 0px; margin-left: 0.5em; }div.foxdiv20141231130126490704 { }body { font-size: 10.5pt; font-family: 'Segoe UI'; color: rgb(0, 0, 0); line-height: 1.5; }</style></head><body>
<div><span></span>Dear Peter,</div><div><br></div><div><span style="font-family: "" segoe="" ui'";="" font-size:="" 14px;="" color:="" rgb(0,="" 0,="" 0);="" background-color:="" rgba(0,="" font-weight:="" normal;="" font-style:="" normal;text-decoration:="" none;'=""> As far as I understand, you would like to calculate a PES with (harmonic) vibrational energy added at each point. I do not believe that is realistic, unless you are talking about an one dimensional reaction path potential along the reaction coordinate, in which other degrees of freedom are optimized and 3N-7 vibrations are obtained. </span><span style="font-family: ''; font-size: 10.5pt; line-height: 1.5; background-color: window;">On a multidimensional PES, otherwise, a normal mode analysis is only physically meaningful at stationary points.</span></div><div><span style="font-family: ''; font-size: 10.5pt; line-height: 1.5; background-color: window;"><br></span></div><div><span style="font-family: ''; font-size: 10.5pt; line-height: 1.5; background-color: window;"> </span><span style="font-family: ''; font-size: 10.5pt; line-height: 1.5; background-color: window;"> If the rate constant is of your interest, you can simply calculate the vibrational frequencies at reactant and the transition state, then do the correction and there are some transition state theory codes to perform such calculations.</span></div><div><span style="font-family: ''; font-size: 10.5pt; line-height: 1.5; background-color: window;"><br></span></div><div><span style="font-family: "" segoe="" ui'";="" font-size:="" 14px;="" color:="" rgb(0,="" 0,="" 0);="" background-color:="" rgb(255,="" 255,="" 255);="" font-weight:="" normal;="" font-style:="" normal;text-decoration:="" none;'=""> I have seen two dimensional minimum energy path surfaces with vibrational energies on the rest of degrees of freedom corrected, reported by the D. C. Clary group. But they have projected out frequencies corresponding to two coordinates in the PES using <span style="font-family: "" segoe="" ui'";="" font-size:="" 14px;="" color:="" rgb(0,="" 0,="" 0);="" background-color:="" rgba(0,="" font-weight:="" normal;="" font-style:="" normal;text-decoration:="" none;'="">CURVILINEAR</span> coordinates which are not straghtforward. Just for your reference.</span></div><div><span style="font-family: "" segoe="" ui'";="" font-size:="" 14px;="" color:="" rgb(0,="" 0,="" 0);="" background-color:="" rgb(255,="" 255,="" 255);="" font-weight:="" normal;="" font-style:="" normal;text-decoration:="" none;'=""><br></span></div><div><span style="font-family: "" segoe="" ui'";="" font-size:="" 14px;="" color:="" rgb(0,="" 0,="" 0);="" background-color:="" rgb(255,="" 255,="" 255);="" font-weight:="" normal;="" font-style:="" normal;text-decoration:="" none;'="">Best, Bin.</span></div>
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<blockquote style="margin-top: 0px; margin-bottom: 0px; margin-left: 0.5em;"><div> </div><div style="border:none;border-top:solid #B5C4DF 1.0pt;padding:3.0pt 0cm 0cm 0cm"><div style="PADDING-RIGHT: 8px; PADDING-LEFT: 8px; FONT-SIZE: 12px;FONT-FAMILY:tahoma;COLOR:#000000; BACKGROUND: #efefef; PADDING-BOTTOM: 8px; PADDING-TOP: 8px"><div><b>From:</b> <a href="mailto:martinspenke@yahoo.de">Martin Spenke</a></div><div><b>Date:</b> 2014-12-30 09:33</div><div><b>To:</b> <a href="mailto:Peter.Reinhardt@upmc.fr">Peter.Reinhardt@upmc.fr</a></div><div><b>CC:</b> <a href="mailto:Molpro-user@molpro.net">Molpro-user@molpro.net</a></div><div><b>Subject:</b> Re: [molpro-user] ZERO POINT ENERGY</div></div></div><div><div class="FoxDiv20141231130126490704"><div style="color:#000; background-color:#fff; font-family:HelveticaNeue, Helvetica Neue, Helvetica, Arial, Lucida Grande, sans-serif;font-size:16px"><div id="yui_3_16_0_1_1419955666725_3362" dir="ltr"><span>Dear Peter, </span></div><div id="yui_3_16_0_1_1419955666725_3362" dir="ltr"><span><br></span></div><div id="yui_3_16_0_1_1419955666725_3362" dir="ltr"><span id="yui_3_16_0_1_1419955666725_3747">The well-defined problem is that the transition structure </span></div><div id="yui_3_16_0_1_1419955666725_3362" dir="ltr"><span id="yui_3_16_0_1_1419955666725_6518">on an enthalpy surface </span>lacks vibrational energy. </div><div id="yui_3_16_0_1_1419955666725_3362" dir="ltr"></div><div id="yui_3_16_0_1_1419955666725_3362" dir="ltr" class="" style="">The usual calculated PES is thus physically an unrealistic surface, therefore </div><div id="yui_3_16_0_1_1419955666725_3362" dir="ltr" class="" style="">the whole PES (namely each point) should be vibrationally</div><div></div><div id="yui_3_16_0_1_1419955666725_3362" dir="ltr">corrected, not only for minimum points but for all.</div><div id="yui_3_16_0_1_1419955666725_3362" dir="ltr"><br></div><div id="yui_3_16_0_1_1419955666725_3362" dir="ltr">I guess i have to calculate for every single point on a full optimized PES,</div><div id="yui_3_16_0_1_1419955666725_3362" dir="ltr">ZPEs and add it to electronic energies afterwards to accomplish the physically realistic one.</div><div id="yui_3_16_0_1_1419955666725_3362" dir="ltr"><br></div><div id="yui_3_16_0_1_1419955666725_3362" dir="ltr">Bests</div><div id="yui_3_16_0_1_1419955666725_3362" dir="ltr">Martin </div><div id="yui_3_16_0_1_1419955666725_3362" dir="ltr"><br></div> <div class="qtdSeparateBR"><br><br></div><div class="yahoo_quoted" style="display: block;"> <div style="font-family: HelveticaNeue, Helvetica Neue, Helvetica, Arial, Lucida Grande, sans-serif; font-size: 16px;"> <div style="font-family: HelveticaNeue, Helvetica Neue, Helvetica, Arial, Lucida Grande, sans-serif; font-size: 16px;"> <div dir="ltr"> <font size="2" face="Arial"> Peter Reinhardt <Peter.Reinhardt@upmc.fr> schrieb am 10:31 Dienstag, 30.Dezember 2014:<br> </font> </div> <br><br> <div class="y_msg_container">Dear Martin,<br clear="none">I'm not sure whether this is a well-defined problem as the zero-point<br clear="none">energy applies to the minimum around which the PES is expanded in a<br clear="none">quadratic form. ZPE concerns the nuclear motion, not the electronic problem.<br clear="none"><br clear="none">Yours,<br clear="none"> Peter<br clear="none"><div class="yqt6121155964" id="yqtfd10606"><br clear="none">Martin Spenke wrote:<br clear="none">> Dear all, <br clear="none">> Is it with molpro possible to calculate PES with the inclusion of zero<br clear="none">> point motion corrections to the energy points of the surface at mrci<br clear="none">> level?If yes, what is the keyword for this ?<br clear="none">> BestsMartin_______________________________________________</div><br clear="none">> Molpro-user mailing list<br clear="none">> <a shape="rect" ymailto="mailto:Molpro-user@molpro.net" href="mailto:Molpro-user@molpro.net">Molpro-user@molpro.net</a><br clear="none">> <a shape="rect" href="http://www.molpro.net/mailman/listinfo/molpro-user" target="_blank">http://www.molpro.net/mailman/listinfo/molpro-user</a><br clear="none"><br clear="none"><br clear="none">-- <br clear="none"> v v v v v v v v v v v v v v v v v v v v v<br clear="none"> > Dr. Peter Reinhardt | Maître de Conférences <<br clear="none"> > Lab. Chimie Théorique | (HDR) <<br clear="none"> > Université P et M Curie | tour 12-13, 4e étage <<br clear="none"> > 4 place Jussieu, case 137 | Tél.: +33(0)1 44 27 9657 <<br clear="none"> > F -- 75252 Paris, France | Fax.: 4117 <<br clear="none"> > email: <a shape="rect" ymailto="mailto:Peter.Reinhardt@upmc.fr" href="mailto:Peter.Reinhardt@upmc.fr">Peter.Reinhardt@upmc.fr</a> <<br clear="none"> > Web: <a shape="rect" href="http://www.lct.jussieu.fr/pagesperso/reinh" target="_blank">http://www.lct.jussieu.fr/pagesperso/reinh </a><div class="yqt6121155964" id="yqtfd72140"> <<br clear="none"> ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^<br clear="none"><br clear="none"></div><br><br></div> </div> </div> </div> </div></div></div></blockquote>
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