Dear Eric,

Yes, the negative barrier is measu= red as deltaE(SCF), deltaH or deltaG and when doing the IRC, I 've foun= d that it connects with the right minima in both sides.=C2=A0

The= problem is that the negative barrier is very huge (about 1000kcal/mol). I = don't know but I think that it's barrierless process??? Am I right?=

Regards

Benoit

Le=C2=A0dim. 14 avr. 2019 =C3=A0=C2=A023:00, Eric V. Patterson eric.patte= rson%x%stonybrook.edu <owner-chemistry-x-ccl.net> a =C3=A9cri= t=C2=A0:

Sent to CCL by: "Eric V. Patterson" [eric.patterson/a\stonybrook.edu<= /a>]
Benoit,

Is the negative barrier measured as deltaE(SCF), deltaH or deltaG?=C2=A0 An= IRC is an E(SCF) thing, so there might be an explanation there.=C2=A0 It i= s definitely possible for thermodynamic corrections to switch the relative = ordering of stationary points that have very similar electronic energies.= =C2=A0 If the IRC goes downhill in both directions and connects to the corr= ect minima, then the stationary points would appear to be correct.

Cheers,
Eric

> On Apr 14, 2019, at 1:13 PM, bonoit bonoit ablux13^^^gmail.com <owner-ch= emistry:+:c= cl.net> wrote:
>
>
> Sent to CCL by: bonoit bonoit [ablux13[*]gmail.com]
> Dear Eric,
>
> Thank you for your response. In fact, I have found a transition state<= br> > with a very very low barrier (under reactants) and I 've checked i= t
> with IRC and it really connects with the corresponding minima of
> reactants and epoxyde product.
>
> Regards
>
> Benoit
>
> 2019-04-14 16:12 UTC+02:00, Eric V. Patterson
> eric.patterson||stonybrook.edu <owner-chemistry^^^ccl.net>:
>>
>> Sent to CCL by: "Eric V. Patterson" [eric.p= atterson_-_stonybrook.edu]
>> Correction:=C2=A0 I did not mean ozonolysis.=C2=A0 I meant mCPBA.<= br> >>
>>> On Apr 14, 2019, at 9:25 AM, Eric V. Patterson
>>> eric.patterson(~)stonybrook.edu <owner-chemistry:+:ccl.net> wr= ote:
>>>
>>>
>>> Sent to CCL by: "Eric V. Patterson" [eric.patterson|= *|st= onybrook.edu]
>>> Dear Benoit,
>>>
>>> Yes, most definitely.=C2=A0 I have done so many times.=C2=A0 N= ow, it would be
>>> helpful to know whether you are trying to model epoxidation vi= a some
>>> process like ozonolysis of an alkene, or whether you are formi= ng the
>>> epoxide from something like a halohydrin.=C2=A0 The latter is = straightforward,
>>> the former less so.
>>>
>>> Best,
>>> Eric
>>>
>>>
>>>> On Apr 14, 2019, at 7:29 AM, Benoit Gearald ablux13-*-gmail.com=
>>>> <owner-chemistry[A]ccl.net> wrote:
>>>>
>>>>
>>>> Sent to CCL by: "Benoit=C2=A0 Gearald" [ablux1= 3---gmail.com]
>>>> Dear CCLers,
>>>>
>>>> Is it possible to locate a transition state for the format= ion of three-
>>>> membered cycle like an epoxyde?
>>>>
>>>> Best regards,
>>>>
>>>> Benoit>
>

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--0000000000003c255005868d0add-- From owner-chemistry@ccl.net Mon Apr 15 08:40:01 2019 From: "Eric V. Patterson eric.patterson#%#stonybrook.edu" To: CCL Subject: CCL: Transition state Message-Id: <-53688-190415083842-24287-gcewh3qkAKEVexaDesrbMg:_:server.ccl.net> X-Original-From: "Eric V. Patterson" Content-Type: multipart/alternative; boundary="Apple-Mail=_4B5FC558-5596-44A7-B47B-19AEE1080481" Date: Mon, 15 Apr 2019 08:38:26 -0400 Mime-Version: 1.0 (Mac OS X Mail 12.4 \(3445.104.8\)) Sent to CCL by: "Eric V. Patterson" [eric.patterson~!~stonybrook.edu] --Apple-Mail=_4B5FC558-5596-44A7-B47B-19AEE1080481 Content-Transfer-Encoding: quoted-printable Content-Type: text/plain; charset=utf-8 Benoit, Something is very wrong. You=E2=80=99re saying that you see a -1000 = kcal/mol change from reactant to TS, deltaE(SCF)? First, that=E2=80=99s = an impossibly large number for a normal chemical reaction and usually = indicates an error in balancing your chemical equation, charge, etc. = Second, that would mean your IRC curve starts 1000 kcal/mol below the = minimum it connects to on the reactant side. In other words, you would = have a steeply positive IRC curve. Again impossible unless a major = mistake has been made. Further, -1000 kcal/mol =3D -1 Mcal/mol =3D an extremely explosive = reaction. You have a mistake somewhere. - Eric > On Apr 15, 2019, at 3:59 AM, bonoit bonoit ablux13-x-gmail.com = wrote: >=20 > Dear Eric, >=20 > Yes, the negative barrier is measured as deltaE(SCF), deltaH or deltaG = and when doing the IRC, I 've found that it connects with the right = minima in both sides.=20 > The problem is that the negative barrier is very huge (about = 1000kcal/mol). I don't know but I think that it's barrierless process??? = Am I right? >=20 > Regards >=20 > Benoit >=20 > Le dim. 14 avr. 2019 =C3=A0 23:00, Eric V. Patterson = eric.patterson%x%stonybrook.edu = > a =C3=A9crit = : >=20 > Sent to CCL by: "Eric V. Patterson" [eric.patterson/a\stonybrook.edu = ] > Benoit, >=20 > Is the negative barrier measured as deltaE(SCF), deltaH or deltaG? An = IRC is an E(SCF) thing, so there might be an explanation there. It is = definitely possible for thermodynamic corrections to switch the relative = ordering of stationary points that have very similar electronic = energies. If the IRC goes downhill in both directions and connects to = the correct minima, then the stationary points would appear to be = correct. >=20 > Cheers, > Eric >=20 > > On Apr 14, 2019, at 1:13 PM, bonoit bonoit ablux13^^^gmail.com =

> wrote: > >=20 > >=20 > > Sent to CCL by: bonoit bonoit [ablux13[*]gmail.com = ] > > Dear Eric, > >=20 > > Thank you for your response. In fact, I have found a transition = state > > with a very very low barrier (under reactants) and I 've checked it > > with IRC and it really connects with the corresponding minima of > > reactants and epoxyde product. > >=20 > > Regards > >=20 > > Benoit > >=20 > > 2019-04-14 16:12 UTC+02:00, Eric V. Patterson > > eric.patterson||stonybrook.edu = >: > >>=20 > >> Sent to CCL by: "Eric V. Patterson" = [eric.patterson_-_stonybrook.edu = ] > >> Correction: I did not mean ozonolysis. I meant mCPBA. > >>=20 > >>> On Apr 14, 2019, at 9:25 AM, Eric V. Patterson > >>> eric.patterson(~)stonybrook.edu = > wrote: > >>>=20 > >>>=20 > >>> Sent to CCL by: "Eric V. Patterson" = [eric.patterson|*|stonybrook.edu ] > >>> Dear Benoit, > >>>=20 > >>> Yes, most definitely. I have done so many times. Now, it would = be > >>> helpful to know whether you are trying to model epoxidation via = some > >>> process like ozonolysis of an alkene, or whether you are forming = the > >>> epoxide from something like a halohydrin. The latter is = straightforward, > >>> the former less so. > >>>=20 > >>> Best, > >>> Eric > >>>=20 > >>>=20 > >>>> On Apr 14, 2019, at 7:29 AM, Benoit Gearald ablux13-*-gmail.com = > >>>> > wrote: > >>>>=20 > >>>>=20 > >>>> Sent to CCL by: "Benoit Gearald" [ablux13---gmail.com = ] > >>>> Dear CCLers, > >>>>=20 > >>>> Is it possible to locate a transition state for the formation of = three- > >>>> membered cycle like an epoxyde? > >>>>=20 > >>>> Best regards, > >>>>=20 > >>>> Benoit>=20 > > >=20 >=20 >=20 > -=3D This is automatically added to each message by the mailing script = =3D- >=20 >=20 >=20 > E-mail to subscribers: CHEMISTRY#ccl.net or = use:= >=20 > E-mail to administrators: CHEMISTRY-REQUEST#ccl.net = or use= >=20 >=20= >=20= >=20=20 > Conferences: = http://server.ccl.net/chemistry/announcements/conferences/ = >=20= >=20 >=20= >=20= >=20 >=20 --Apple-Mail=_4B5FC558-5596-44A7-B47B-19AEE1080481 Content-Transfer-Encoding: quoted-printable Content-Type: text/html; charset=utf-8 Benoit,

Something is very wrong. You=E2=80=99re saying that you = see a -1000 kcal/mol change from reactant to TS, deltaE(SCF)? = First, that=E2=80=99s an impossibly large number for a normal = chemical reaction and usually indicates an error in balancing your = chemical equation, charge, etc. Second, that would mean your IRC = curve starts 1000 kcal/mol below the minimum it connects to on the = reactant side. In other words, you would have a steeply positive = IRC curve. Again impossible unless a major mistake has been = made.

Further, = -1000 kcal/mol =3D -1 Mcal/mol =3D an extremely explosive = reaction.

You = have a mistake somewhere.

- Eric

On Apr 15, 2019, at 3:59 AM, bonoit bonoit ablux13-x-gmail.com = <owner-chemistry,ccl.net> wrote:

Dear Eric,

Yes, = the negative barrier is measured as deltaE(SCF), deltaH or deltaG and = when doing the IRC, I 've found that it connects with the right minima = in both sides.
The problem is that the = negative barrier is very huge (about 1000kcal/mol). I don't know but I = think that it's barrierless process??? Am I right?

Regards

Benoit

Le dim. = 14 avr. 2019 =C3=A0 23:00, Eric V. Patterson eric.patterson%x%stonybrook.edu <owner-chemistry#ccl.net> a =C3=A9crit :

Sent to CCL by: "Eric V. Patterson" [eric.patterson/a\stonybrook.edu]
Benoit,

Is the negative barrier measured as deltaE(SCF), deltaH or deltaG? = An IRC is an E(SCF) thing, so there might be an explanation there. = It is definitely possible for thermodynamic corrections to switch the = relative ordering of stationary points that have very similar electronic = energies. If the IRC goes downhill in both directions and connects = to the correct minima, then the stationary points would appear to be = correct.

Cheers,
Eric

> On Apr 14, 2019, at 1:13 PM, bonoit bonoit ablux13^^^gmail.com <owner-chemistry:+:ccl.net> = wrote:
>
>
> Sent to CCL by: bonoit bonoit [ablux13[*]gmail.com]
> Dear Eric,
>
> Thank you for your response. In fact, I have found a transition = state
> with a very very low barrier (under reactants) and I 've checked = it
> with IRC and it really connects with the corresponding minima of
> reactants and epoxyde product.
>
> Regards
>
> Benoit
>
> 2019-04-14 16:12 UTC+02:00, Eric V. Patterson
> eric.patterson||stonybrook.edu = <owner-chemistry^^^ccl.net>:
>>
>> Sent to CCL by: "Eric V. Patterson" [eric.patterson_-_stonybrook.edu]
>> Correction: I did not mean ozonolysis. I meant = mCPBA.
>>
>>> On Apr 14, 2019, at 9:25 AM, Eric V. Patterson
= >>> eric.patterson(~)stonybrook.edu = <owner-chemistry:+:ccl.net> wrote:
>>>
>>>
>>> Sent to CCL by: "Eric V. Patterson" [eric.patterson|*|stonybrook.edu]
>>> Dear Benoit,
>>>
>>> Yes, most definitely. I have done so many = times. Now, it would be
>>> helpful to know whether you are trying to model epoxidation = via some
>>> process like ozonolysis of an alkene, or whether you are = forming the
>>> epoxide from something like a halohydrin. The latter = is straightforward,
>>> the former less so.
>>>
>>> Best,
>>> Eric
>>>
>>>
>>>> On Apr 14, 2019, at 7:29 AM, Benoit Gearald = ablux13-*-gmail.com
>>>> <owner-chemistry[A]ccl.net> = wrote:
>>>>
>>>>
>>>> Sent to CCL by: "Benoit Gearald" [ablux13---gmail.com]
>>>> Dear CCLers,
>>>>
>>>> Is it possible to locate a transition state for the = formation of three-
>>>> membered cycle like an epoxyde?
>>>>
>>>> Best regards,
>>>>
>>>> Benoit>
>

-=3D This is automatically added to each message by the mailing script = =3D-

E-mail to subscribers: CHEMISTRY#ccl.net or use:
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=
Before posting, check wait time at: http://www.ccl.net

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Search Messages: http://www.ccl.net/chemistry/searchccl/index.shtml

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= --Apple-Mail=_4B5FC558-5596-44A7-B47B-19AEE1080481-- From owner-chemistry@ccl.net Mon Apr 15 10:04:01 2019 From: "Arturo Espinosa artuesp!^!um.es" To: CCL Subject: CCL: Transition state Message-Id: <-53689-190414201706-10459-ok1QO1jr/7O2lUKQkLfXEA_-_server.ccl.net> X-Original-From: Arturo Espinosa Content-Language: es-ES Content-Type: multipart/alternative; boundary="------------DD4F10B9336FF6D1B5F21959" Date: Mon, 15 Apr 2019 02:16:48 +0200 MIME-Version: 1.0 Sent to CCL by: Arturo Espinosa [artuesp a um.es] This is a multi-part message in MIME format. --------------DD4F10B9336FF6D1B5F21959 Content-Type: text/plain; charset=utf-8; format=flowed Content-Transfer-Encoding: 8bit Dear Benoit, in /Inorg. Chem./*2018*, /57/, 8058, a low barrier cyclitation of a carbonyl ylide to an oxirane (the inverse process of the heterolytic oxirane C-C bond cleavage) is described. Regards, Arturo El 14/04/2019 a las 13:29, Benoit Gearald ablux13-*-gmail.com escribió: > Sent to CCL by: "Benoit Gearald" [ablux13---gmail.com] > Dear CCLers, > > Is it possible to locate a transition state for the formation of three- > membered cycle like an epoxyde? > > Best regards, > > Benoit> > -- ------------------------------------------------------------------------ /*Dr. Arturo Espinosa **Ferao* Professor of Organic Chemistry Depto. de Química Orgánica, Facultad de Química Campus de Espinardo, Universidad de Murcia E-30071 Murcia (Spain) Phone: + 34 868 88 7489 Fax: + 34 868 88 4149 e-mail address: //artuesp++um.es/ /Website: http://www.um.es/funcmolecmat/artuesp// --- El software de antivirus Avast ha analizado este correo electrónico en busca de virus. https://www.avast.com/antivirus --------------DD4F10B9336FF6D1B5F21959 Content-Type: text/html; charset=utf-8 Content-Transfer-Encoding: base64 PGh0bWw+DQogIDxoZWFkPg0KICAgIDxtZXRhIGh0dHAtZXF1aXY9IkNvbnRlbnQtVHlwZSIgY29u 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