From owner-chemistry@ccl.net Wed Jun 14 12:29:00 2017 From: "Ivan Franzoni ivan.franzoni[A]utoronto.ca" To: CCL Subject: CCL: Correction on single-point energies Message-Id: <-52846-170614113536-11827-u1JLd+H3QOyfWbotyeBbDw%%server.ccl.net> X-Original-From: "Ivan Franzoni" Date: Wed, 14 Jun 2017 11:35:35 -0400 Sent to CCL by: "Ivan Franzoni" [ivan.franzoni * utoronto.ca] Hello! I am computing the energy of a transition-metal catalyzed organic reaction. I optimized all the intermediates and transition states in gas-phase at the BP86/6-31G**/LANL2DZ level of theory and performed frequency analysis to confirm the nature of all stationary points. I next run single point calculations in toluene at the M06L/6-311G**/SDDALL level of theory and also repeated a new frequency analysis. I saw that someone uses energy and zero-point, enthalpies and free energies corrections from the SP calculation in solvent. In other cases someone uses the total energy obtained in solvent and add the correction previously obtained in gas-phase (so no frequency analysis on the single point calculation). Can anyone comment of these different approaches and maybe suggest which one is the best? Thank you, Ivan Franzoni UofT From owner-chemistry@ccl.net Wed Jun 14 13:48:01 2017 From: "Eric Hermes erichermes%gmail.com" To: CCL Subject: CCL: Correction on single-point energies Message-Id: <-52847-170614132706-1449-V6NwxOS8y3D/m3MROdJqeA(_)server.ccl.net> X-Original-From: Eric Hermes Content-Transfer-Encoding: 8bit Content-Type: text/plain; charset="UTF-8" Date: Wed, 14 Jun 2017 12:26:59 -0500 Mime-Version: 1.0 Sent to CCL by: Eric Hermes [erichermes-x-gmail.com] Ivan, There is an argument to be made whether the gas-phase or solution-phase frequencies are more appropriate to use for the calculation of free energy of a species in solution, but I will not comment on which approach is "better" or "more physical". However, frequencies calculated at anything other than the minimum- energy geometry are not physically meaningful. While you have minimized the geometry on your BP86/6-31G**/LANL2DZ/gas-phase potential energy surface, this is not guaranteed to be (and in general is not going to be) a minimum-energy geometry on the M06L/6-311G**/SDDALL/toluene potential energy surface. So, performing a frequency calculation on the latter system without relaxation is not going to result in physically meaningful frequencies. If you are concerned that frequencies calculated with the lower level of theory are going to be insufficiently accurate, you will need to precede any frequency calculations at a higher level of theory with a geometry minimization at that same level of theory. Eric On Wed, 2017-06-14 at 11:35 -0400, Ivan Franzoni ivan.franzoni[A]utoronto.ca wrote: > Sent to CCL by: "Ivan  Franzoni" [ivan.franzoni * utoronto.ca] > Hello! > > I am computing the energy of a transition-metal catalyzed organic > reaction. > I optimized all the intermediates and transition states in gas-phase > at the > BP86/6-31G**/LANL2DZ level of theory and performed frequency analysis > to > confirm the nature of all stationary points. I next run single point > calculations in toluene at the M06L/6-311G**/SDDALL level of theory > and > also repeated a new frequency analysis. > I saw that someone uses energy and zero-point, enthalpies and free > energies > corrections from the SP calculation in solvent. In other cases > someone uses > the total energy obtained in solvent and add the correction > previously > obtained in gas-phase (so no frequency analysis on the single point > calculation). > Can anyone comment of these different approaches and maybe suggest > which > one is the best? > > Thank you, > > Ivan Franzoni > UofT > > > > -= This is automatically added to each message by the mailing script > =- > To recover the email address of the author of the message, please > change>       http://www.ccl.net/cgi-bin/ccl/send_ccl_message>       http://www.ccl.net/cgi-bin/ccl/send_ccl_message > > Subscribe/Unsubscribe:  >       http://www.ccl.net/chemistry/sub_unsub.shtml> > Job: http://www.ccl.net/jobs  > Conferences: http://server.ccl.net/chemistry/announcements/conference > s/>       http://www.ccl.net/spammers.txt> > From owner-chemistry@ccl.net Wed Jun 14 14:23:01 2017 From: "Norrby, Per-Ola Per-Ola.Norrby=astrazeneca.com" To: CCL Subject: CCL: Correction on single-point energies Message-Id: <-52848-170614133025-2521-qHjL3+/188AUscfZwe7WaQ[*]server.ccl.net> X-Original-From: "Norrby, Per-Ola" Content-Language: en-US Content-Transfer-Encoding: 8bit Content-Type: text/plain; charset="us-ascii" Date: Wed, 14 Jun 2017 17:30:13 +0000 MIME-Version: 1.0 Sent to CCL by: "Norrby, Per-Ola" [Per-Ola.Norrby _ astrazeneca.com] Hi Ivan, Using frequencies from a different level is NEVER correct. The equations for thermodynamic terms are ONLY valid at a stationary point, and you'll not be at a true minimum unless you optimized at the same level of theory. Per-Ola Sent from my iPhone > On 14 Jun 2017, at 19:00, Ivan Franzoni ivan.franzoni[A]utoronto.ca wrote: > > > Sent to CCL by: "Ivan Franzoni" [ivan.franzoni * utoronto.ca] > Hello! > > I am computing the energy of a transition-metal catalyzed organic reaction. > I optimized all the intermediates and transition states in gas-phase at the > BP86/6-31G**/LANL2DZ level of theory and performed frequency analysis to > confirm the nature of all stationary points. I next run single point > calculations in toluene at the M06L/6-311G**/SDDALL level of theory and > also repeated a new frequency analysis. > I saw that someone uses energy and zero-point, enthalpies and free energies > corrections from the SP calculation in solvent. In other cases someone uses > the total energy obtained in solvent and add the correction previously > obtained in gas-phase (so no frequency analysis on the single point > calculation). > Can anyone comment of these different approaches and maybe suggest which > one is the best? > > Thank you, > > Ivan Franzoni > UofT> https://clicktime.symantec.com/a/1/k0Yv3ZiwM3GXQN5rtNUFPvMj4pv3K3j6wql0QGfM0TI=?d=QRzRqjstCLkmQpYqoqi6-x8mC7BgkEquPvWf7W1A3zZk_ZNRLD_FuGePsUB4JyxV5tYhZo8dsS2m97qt1cr9Lvx7sAQ_ndF_xwm8dEhr3mtWwZ5SSQLC-JKqKHKBRdwOPueVlnZVPa_GFS8aV7MRNGyOdV-qcBWp4do-glhNY7ayXqIvStDp3BGvb4fO2bYtmRQyavl6UVM47BcEyQX1Er6hyw38KFsam9Hsn7-3DPkNVKejIt1uFYht0DpIlncvi32EyAw3hYfybAs2-_Q1_fgxhCiuZrAIRQVkkWyOVYKK6Evl5Je7RGC55AhI1dQU-IdZ_Wo67yA6OYpojWiIQEzJFIZpyaA-9eMGBYun-JNDI0FrR-b7t4NXHfJFnzPYAsFOOMQHAjjDNjD_Yh-0vFErzCpMOOjoRMn6J4stAySHNzavAW7hXNno4dyJ1ztlXkFIJNRo6fgB&u=http%3A%2F%2Fwww.ccl.net%2Fcgi-bin%2Fccl%2Fsend_ccl_message> 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