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text:
Grabow Deal Near Completion
Bruce Levine is reporting that a deal with John Grabow should be completed today for two years and nearly 7.5 million. I had expressed my indifference in the past over resigning Grabow. Oh sure, his ERA has been pretty good the last two years, but with a BB/9 rate near 5 last year and 4.15 for his career, I don't think anyone would really miss him if he got away. I was asked in the comments yesterday how I'd handle this situation and here was my response.
I offer Grabow arbitration and wait to see if he takes it...chances are
he will because a team doesn't want to give up a draft pick for a
set-up man(ed. note - Grabow is classified as a Type A free agent). That'll cost the Cubs probably an extra $1M this year, but
if Ricketts is serious about propping the farm system, he'll roll the
dice(ed. note - when I say Ricketts, I mean they'll offer to cover Hendry's budget if Grabow wins a big arbitration case). Maybe the Cubs get lucky and a team with a protected pick signs
him or one that signed a few other FA's and the Cubs score some extra
draft picks. If he does sign with another team, I wait until February
when inevitably some lefties will still be around and sign one or two
on the cheap. I imagine you can find a few on the trade market for Jake
Fox who will likely be traded, since he's out of options and in Lou's
In general, I could care less if the Cubs have even one lefty in
their pen. It's a stupid unnecessary crutch for a manager so he can
make safe moves that the media won't blast him on. The Angels did
plenty good for awhile with their pen with no lefties (before Oliver
and Fuentes). Better off finding good relievers that can get guys from
both sides of the plate and you'll trust for an inning or longer. Cubs
had a great LOOGY in Ohman and couldn't figure out to use him.1
And I don't mind Grabow, he can get guys from both sides of the
plate, I just think's just slightly above average and I'm also not sure
Lou will use him properly, which is a full inning at a time, rather
than a match-up lefty.
Now when I wrote that, I figured Grabow could get anywhere from $4-$5M in arbitration case due to the 2.84 and 3.36 ERA's the last two years, near the top in holds, a handful of saves and Type A free agent classification. That would be a hefty raise from the $2.3M he made in 2008.
But I looked a little further at contracts signed by set-up men and relievers last year and I probably guessed a little high.
Jeremy Affeldt - 2 years/$8M total
Juan Cruz - 2 years/$6M total (there's a $4M 2011 option or $500K buyout, so $6.5M guaranteed)
Kyle Farnsworth - 2 years/$8.75M (there's a $5.25M 2011 option or $500K buyout, so $9.25M guaranteed plus incentives that could earn him more)2
Joe Beimel - 1 year/$2M
Will Ohman - 1 year/$1.35M
Latroy Hawkins - 1 year/$3.5M
I think Affeldt might be the best comp for Grabow, coming off two good seasons before 2009 and in his first year of free agency and both pitchers don't show much of a disparity between getting righties or lefties out. So at the high end, we could expect Grabow to maybe get $4M in arbitration.
Considering that assumption and considering that relievers tend to be rather volatile from year-to-year, it would seem like a good idea to not tie yourself up to a multi-year offer if you don't have to unless you feel you're getting a pretty good discount or certain that Grabow could deliver two good seasons in a row. Now we don't know the contract specifics quite yet, but at an average of $3.75M per year, Hendry looks to be paying the top of the scale and doing it for two years now, when he probably could have gotten away with just one by offering arbitration. Now maybe the deal will be one of Hendry's famous back-loaded deals as the Cubs have money coming off the books next year, but I fail to see how the Cubs aren't doing anything but paying at the top of payscale range here for Grabow's services.
So then can the Cubs safely assume that he'll continue to pitch well the next two years? Well I certainly don't think you can assume that at all. His career ERA is 4.05 and his career FIP is 4.18 including 4.54 in 2008 and 4.20 in 2009 amidst the two seasons that will have earned him this new deal. That doesn't instill a lot of confidence in me that he can repeat what he's been doing, although that's not to say that he won't. It just indicates to me that Grabow is probably nothing special amongst his fraternity of relievers and not someone that warranted a multi-year deal. And when you have a player that isn't particularly special and have the opportunity to sign him to a one-year deal instead of two, I think you take that opportunity. Of course, the Cubs could have lost Grabow to free agency, but the potential of getting two extra draft picks is worth that risk.
1 - speaking of my left-handed bullpen crutch rant, this was Grabow's 2007 entry in Baseball Prospectus which I found on his PECOTA page. Now Grabow isn't what many would consider a LOOGY, but getting lefties out will be very much one of his primary roles on the team.
You can make a strong argument that no team needs a LOOGY. Mike
Scioscia won 92 games and a division title in 2004 without having a
lefty reliever on his team. LOOGies do more harm than good because they
end up facing just as many righties than lefties as a result of walks
and pinch-hitters, and take up precious roster space without providing
enough innings
2 - Points and laughs at Royals
Re: Grabow Deal Near Completion
Wittenmeyer tweets deal is done...
cst_cubs: Grabow, Cubs reach agreement on 2yr deal.
Re: Grabow Deal Near Completion
WOW! Another mediocre middle reliever! That goes great with our below average first baseman and our overpaid and underachieving outfield. Now all we need is a shortstop, second baseman and some starting pitching and we will be able to compete in our own division! I guess we are "rebuilding" again. How about getting a real closer, getting rid of Z and finding some WINNERS!!!
Re: Grabow Deal Near Completion
Re: Lowe or Vazquez on the block
His approach is to not insinuate that a player is gone no matter what. He has to leave at least a thread of persuasion out there that if they won't release him if they cannot move him. My guess is that Hendry sucks at poker.
Re: Grabow Deal Near Completion
Any news on the Koyie Hill contract extension?
Re: Grabow Deal Near Completion
The Fangraphs guy says the Grabow deal is "a waste of cash", which I find ridiculous given how his website is "a waste of time"
According to Fangraphs, Grabow was worth $3, while Jose Guillen was worth $74 million last year.
Re: Grabow Deal Near Completion
Not sure where you found those numbers. Says that Grabow was worth $1.0 and Guillen was negative $8.8 last year.
Re: Grabow Deal Near Completion
No offense, but this is assinine:
"You can make a strong argument that no team needs a LOOGY. Mike Scioscia won 92 games and a division title in 2004 without having a lefty reliever on his team."
There are 8 playoff teams a year. So one team of eighty in a decade made the playoffs (and didn't go anywhere in them)is some kind of compelling evidence that LOOGY's are required? It's actually evidence of the opposite.
Grabow isn't a LOOGY, anyway. How often are there playoff teams where the highest salaried guys are two first year Arb guys (Marmol and Marshall)?
Just looking at innings and R/L splits also negates the concept of leverage. Who was the #1 ranked non-closer in terms of expected wins above replacement? Left handed setup guy Matt Thornton. Who was #3? Jeremy Affeldt.
The FIP numbers are scary, though.
Re: Grabow Deal Near Completion
If the Angels did it for the entire decade, the point still holds.
Where does Fangraphs get their WAR values from? BP says that Grabow was worth 3 wins last year... If 5.3 wins of Derrek Lee is worth $23.9 million, then 3 wins of Grabow is worth $13.5 million.
Who are the relievers that the Cubs are going to get who are better than Grabow for 2 years at $3.75 million per.
Your thing about reliever volatility doesn't make any sense by the way. Volatility can go both ways, and Grabow isn't getting his deal based solely on one year.
Re: Grabow Deal Near Completion
BP fixed their replacement level problem like a year ago. I assume that the Fangraphs stuff is from BP because WAR is a BP developed concept. The problem is that BP guys themselves use the XWLR (or whatever) for relievers, not WAR, but so Fangraphs is using the incorrect metric according to their source.
The issue of BP using context weighted metrics for relievers, but not for starters and positioned players is still unresolved.
Are you saying that Grabow's true talent level is represented by his FIP and not his ERA? That's a valid argument, but to just say "relievers are volatile, therefore don't give them multi-year deals" doesn't make sense. In short, if he's worth $3.75 for a year, he's worth $7.5 for two. If he has a 5 ERA next year and a 2 ERA in 2011, that would be volatility, wouldn't it? It would also mean that the two year deal was the correct decision (over a 1 year deal).
Re: Grabow Deal Near Completion
Thanks for the link. Fangraphs WAR is a veritable mindfield of wrongness.
Apparently their $Values are also incorrect.
Re: Grabow Deal Near Completion
"fangraphs article is pretty much the way I feel"
"and I don't recall ever using WAR in this discussion fwiw... "
Re: Grabow Deal Near Completion
What is it good for?
Absolutely nothing......
Re: Grabow Deal Near Completion
Good God, y'all.
Re: Grabow Deal Near Completion
I love that song.
Re: Grabow Deal Near Completion
OK, I'll take your word for it.
Re: Grabow Deal Near Completion
"And the risk of losing him to free agency is outweighed by the getting draft picks for him and another John Grabow isn't hard to find. "
OK, stop there. When you start talking about volatility then you're undermining and confusing your own argument.
Re: Grabow Deal Near Completion
Mature and articulate...
Re: Grabow Deal Near Completion
No offense, but this is assinine:
"You can make a strong argument that no team needs a LOOGY. Mike Scioscia won 92 games and a division title in 2004 without having a lefty reliever on his team."
There are 8 playoff teams a year. So one team of eighty in a decade made the playoffs (and didn't go anywhere in them)is some kind of compelling evidence that LOOGY's are required? It's actually evidence of the opposite.
I think you meant "aren't" instead of "are" in your last question? If so I think your premise needs to be more broadly applied. One team in 80 does not show that LOOGYs are not required. Correct. But no one has shown that only one team in 80 were LOOGY-less.
That is, I don't think anyone has yet shown here that LOOGYs are or are not required. That would be a broader study. But that the Angels apparently went without one and were successful suggests another team may be able to do likewise.
Re: Grabow Deal Near Completion
Yes, that was a typo. But the point remains, that one team in 80 or as Rob G went on to whine one team in 14 isn't a compelling argument. You get 25 men on the roster. Probably 16 of them are without a doubt major contributors. With the remaining 9, you probably have 3 who are just there to finish out hopeless games and 6 who are there to help you win games. Having a reliever, left handed or right handed who can help you win those games (used properly in high leverage situations) is a good thing.
Re: Grabow Deal Near Completion
Nic Cage thinks that Hendry isn't very good with a Budget.
Re: Grabow Deal Near Completion
Bob Nightengale now of usa today says Bradley still being considered by Rays
Re: Grabow Deal Near Completion
Props to Rob G. Lincecum wins the Cy.
Re: Grabow Deal Near Completion
Wainwright gets most 1st place votes, so it does appear Lincecum wins due to the split between Carpenter and Wainwright.
Re: Grabow Deal Near Completion
Noting that Linci was caught using ganja, could it be said he might have been "hungrier" than the other pitchers?
Re: Grabow Deal Near Completion
Re: Grabow Deal Near Completion
Hendry gave both Howry and Eyre 3 year deals back in 2006 (both in the 3/9 range if I recall)...so at least he's learned setup relievers don't warrant 3 year contracts (based on how Lou wrecked JH's Stevie Eyre experience).
So I'll chalk this as a small improvement in the Hendry learning curve... for those of us who are looking for a wildflower growing in a toxic dump.
Re: Grabow Deal Near Completion
I wonder if Jim Hendry has explored buying up Randy Wells arbitration years?
5/40 range with a NTC should probably get it done. Maybe a player option year 6 in the 11-12 range?
Re: Grabow Deal Near Completion
$1 million
$2 million
$3 million
$5 million
$8 million
That's $19 milion of the next 5 years of Wells. $40 million would be
$6 million
$7 million
$8 million
$9 million
$10 million
That may be a bit much.
Re: Grabow Deal Near Completion
It was
Re: Grabow Deal Near Completion
Missed, it. Your player evaluations are a bit hard to keep track of.
Re: Grabow Deal Near Completion
Because they are always spot on?
Re: Grabow Deal Near Completion
now that's sarcasm.
Re: Bradley wins an award...
Someone should introduce Posnanski to a guy names Alfonso Soriano.
Re: Grabow Deal Near Completion
We need to make a distinction between Grabow's former role (and the value attached to that role) and the role that Hendry sees him performing under this contract.
Grabow apparently will be used as the primary 8th inning set-up man, facing both righty and lefty hitters. He may also be used as the closer when Marmol goes through one of his control lapses. Since Marmol and Guzman both come with question marks, Grabow serves as the only proven member at the back of the pen.
If this is indeed the case, then Grabow has a heightened value to Hendry and the Cubs than that of a normal set-up man, and certainly more than a run-of-the-mill LOOGY or middle reliever.
Re: Grabow Deal Near Completion
The role shouldn't have any bearing at this point.
I doubt that Hendry is giving Guzman or Marmol Free Agent closer money at this point.
The reason I've bitched about it, is that it is yet another example of Hendry bidding against himself. He had the hammer. He can go year to year forever with Grabow. Make a guy earn his money. Don't be such a vagina at the negotiating table Jimbo.
Re: Grabow Deal Near Completion
Marmol continues to implode, Grabow takes over the close roll gets 38 saves and has a 2.85 ERA leading helping the Cubs to the playoffs.
What's Grabow's 2011 salary?
Before Grabow has to accept arbitration he gets signed by the Yankees who have also signed Lackey and Holliday.
Gaub and Parker can't hold down the setup role, and our bullpen is a mess all year. We then have to trade Brett Jackson for a setup man at the deadline.
There's risk on both sides of the guaranteed contract equation.
Re: Grabow Deal Near Completion
Or the much more likely scenerio
Grabow reverts back to career norms.
Continues to walk 5 per 9 and Lou completely loses faith in him
Grabow gets the Stevie Eyre treatment of mop-up work, While Lou bitches that we don't have a reliable lefty.
Jim Hendry eats the 2nd year of the deal and trades Grabow somewhere for a middling A ball "Prospect/suspect"
Re: Grabow Deal Near Completion
These things are possible as well, but it's nonsensical to automatically dismiss any other scenario from the realm of possibility.
Re: Grabow Deal Near Completion
In close Cy Young voting, Lincecum was one toke over the line?
Ta da boom.
Re: Grabow Deal Near Completion
Angels, Dodgers and Rays announced their 40 man roster additions this afternoon, so Cubs moves should be announced shortly, not sure when the last minute is though.
Re: Grabow Deal Near Completion
Per Muskat tweet: Heilman traded to Snakes for 2 prospects!
CarrieMuskat: #cubs deal Aaron Heilman to D-backs for two Minor League prospects
Re: Grabow Deal Near Completion
Yay! are they real prospects or just two bodies?
Re: Grabow Deal Near Completion
Seriously, who cares?
Re: Grabow Deal Near Completion
Considering that I asked...do you still need an answer to that question? But thanks for taking the time to not answer.
Re: Grabow Deal Near Completion
My point, much too obtuse for your seven functioning synapses to grasp, is that anything, even nothing, is better than paying Heilmann next year.
We got the next Mickey Mantle and Joe Jackson in the trade. Celebrate.
Re: Grabow Deal Near Completion
You're awesome.
That's sarcasm.
Re: Grabow Deal Near Completion
But don't you want to know how I finished in my fantasy leagues?
Re: Grabow Deal Near Completion
Oh good, I was hoping there was more. Does the asshole treatment work in your daily life as well? or does the cowardice of anonymity drive you?
I'm anxiously awaiting your next expression of wit.
Re: Grabow Deal Near Completion
I haven't had the asshole treatment, what did they dip you in?
How about next time instead of jumping to conclusions, you just, you know, be cool? You're the one who picked this fight.
Re: Grabow Deal Near Completion
Totally worth the wait.
Re: Grabow Deal Near Completion
I am glad you liked it. I have to feel sorry for the people who come across your path on a daily basis. Or where you live do people they enjoy people with martyr complexes who swear at you because they're too thick to get a joke and then act like they're the aggrieved party? Yeah, you must be a barrel of monkeys.
Go ahead and post your name, address and put your Facebook page to public and I'll do the same.
Re: Grabow Deal Near Completion
Your summary of our dialogue is perfect. I can neither add nor subtract from it. You are the Revelation of internet dialogue! I'll just leave it with a complete acceptance of your views.
I'm going to pass for now on your request for Facebook friendship. While I'd welcome your wit in all aspects of my life, I feel that my friends, who prefer martyr-types, might not understand your level of brilliant humor. Neither am I particularly interested in a new penpal. I sponsor several dozen Kenyan children and can barely keep track of my 'pals' as is! Thank you for requesting my friendship, though.
Re: Grabow Deal Near Completion
Well, at least we know who is being an ass with the safeguard of his internat anominonity now.
Please let us all know when you emerge from your mom's basement with the breathtaking details of your latest fantasy league championship.
Re: Grabow Deal Near Completion
Guys -- chill.
Re: Grabow Deal Near Completion
Fox says the Cubs obtained minor leaguers Scott Maine and Ryne White in return.
Link not working yet
Re: Grabow Deal Near Completion
And the Heilman move clears 40 man roster space
Re: Grabow Deal Near Completion
PWSullivan: Cubs sent Heilman to D'backs for prospects instead of non-tendering him. http://bit.ly/drHzv
The Cubs sent reliever Aaron Heilman to Arizona on Thursday for a pair of minor-league prospects.
Heilman didn't figure into the Cubs 2010 plans, and was likely to be non-tendered by the club next month.
In return, the Cubs received left-handed reliever Scott Maine, who went 4-5 with seven saves and a 2.90 ERA at Double-A Mobile and Triple-A Reno, and first baseman Ryne White, who hit .266 with six homers and 52 RBI at Class-A Visalia.
Re: Grabow Deal Near Completion
I have a feeling we're going to end up a couple pitchers short this year.
Randy Wells #3 Starter
Ted Lilly injury
Mitch Adkins and Jeff Eyechart as the #6 and 7 starters
Guzman,Grabow,Marmol as the backend of the bullpen
Just doesn't seem like much margin for injury or error.
Re: Grabow Deal Near Completion
HOW DO YOU LIKE THAT, Cubster?!!
Re: Grabow Deal Near Completion
In return, the Cubs received left-handed reliever Scott Maine, who went 4-5 with seven saves and a 2.90 ERA at Double-A Mobile and Triple-A Reno
I wonder if we just traded for the next John Grabow.
Re: Grabow Deal Near Completion
everybody is so testy here lately
I like both moves, but I hope it's not Hendry easing us up for his wtf move (Pat Burrel)
Re: Grabow Deal Near Completion
Submitted by Cubster on Thu, 11/19/2009 - 3:25pm.
Angels, Dodgers and Rays announced their 40 man roster additions this afternoon, so Cubs moves should be announced shortly, not sure when the last minute is though.
CUBSTER: MLB and minor league reserve lists must be submitted to the MLB office by close of business tomorrow (Friday). Also, all players on an MLB 60-day DL must be reactivated no later than the day after the end of the MLB Free-Agency Filing Period, which is also tomorrow. (I believe about five clubs still have players on the 60-day DL). And any MLB Article XX FA who signs a major league contract after today gets an automatic NTC through June 15th, even if the player re-signs with his former club.
Recent comments
J-Hey not finishing with an offensive onslaught.
If Geoff Blum could be a Playoff hero, there is hope still...
Giants scare me. I think you're wrong about Bumgarner, he would pitch on short rest for Game 2 and then full rest for Game 5. Cueto would go Game 1, then short rest in game 4. Add in some really tough outs in that lineup and I want nothing to do with them. With that rotation they can easily steal a series.
Cards are a tough matchup. The rivalry evens out their comparable lack of talent. And like someone said, they love HRs, which is how to beat the Cubs. The upside is that I would feel really good about Lester twice against STL.
j.buchanan with a nice start...5ip 2h 1bb 3k, 0r/er
zobrist with 2HR and a double through 8
heyward 0-4 :(
Mark Gonzales @MDGonzales
Soler likely to return Sunday, Maddon says
Right now, I'd like to see the Mets first, Giants 2nd.
I believe that since most of the team from last years' NLCS is on the squad this year, they will really amp their game up even more to kick their ass in payback for 2015.
The Giants just do not have the depth in years past, and I think all things equal - and at Wrigley - they could handle them.
I do not want to see the Cards, period. Or their fans, media, or Joe Buck.
I don't want to play Braves in the first round. Any friggin team in the league can win 3 of 5..I hate the first round. Furthermore, I wanted to play the Marlins in 2003 and the Mets over Dodgers last year.
With that said in reverse order:
3. Cardinals: It will be devastating to lose in the first round, but even worse to their main rival. It is increased incentive for the Cardinals, especially after last year. Cards would have nothing to lose, Cubs have everything to lose.
2. Giants: Rotation in the playoffs scare me a bit, but what a lousy team.
1. Mets--because of the losses in the rotation
2. Giants--because they're not the team they were BUT they maybe have bullshit even-year magic?
3. Cardinals--because rivalry and not making the playoffs hurts them more than losing in the NLDS plus getting eliminated by them in the playoffs would make for horrible sports commentary next throughout next season.
Who's asking?
CLE/DET rained out last night already, possible rain-outs in New York (vs. Baltimore), Boston(vs. Toronto) and Philly(vs. Mets) this weekend too.
Not only games involving playoff spots that would need to be played, but any that involve home field advantage.
I got the first one! Second one I'm not even sure what even/odd betting is.
any opponent preference for NLDS?
Mets are down to 1 great pitcher instead of 4. Syndegaard may pitch Sunday which means if Mets win the WC game, he'd be set up for Game 1. There's a chance they clinch a spot by Sunday so he'd pitch the WC and then we'd probably get Colon for Game 1. They've certainly had the hottest bats over the last week and month out of the WC options.
A couple of Cub related puzzles.
Can't teach height and thinness
Hopefully Pirates don't call up A. Lincoln.
j.buchanan going friday...should be...baseball...or something like it.
Wow. I didn't know they could do that.
Nice for Willson, not so much for Addy.

subset: commoncrawl


text:
|Senior Associate Athletics Director for Peak Performance
|Alma Mater:
|William & Mary
|Graduating Year:
|12 Years
Drew Galbraith came to Dartmouth in 2004 and moved into the role of Senior Associate Athletics Director for Peak Performance in 2011. As head of Dartmouth Peak Performance, he coordinates programs designed to position student-athletes to achieve the highest levels of physical, intellectual and personal growth during their Dartmouth career. Galbraith also serves as a liaison to health professionals who work with Dartmouth student-athletes, including Dartmouth Health Services and physicians from Dartmouth-Hitchcock Medical Center.
Galbraith arrived as Associate Athletics Director for Compliance and Administration and filled additional roles before being named Senior Associate Athletics Director in 2008. He has overseen the student services areas since his arrival.
He also serves as sport administrator for football and DP2 and is a member of the department's senior leadership team.
Galbraith recently finished a six-year term on the NCAA Skiing Committee and serves on the NCAA Administration Cabinet. In 2014, he was appointed chair of the NCAA Division I Men's Soccer Committee for the first of two years.
After starting his professional career in media relations and broadcasting at William & Mary then Virginia Commonwealth, Galbraith then completed stints in compliance at both William & Mary and Nebraska Omaha.
He earned both his B.A. (1995) and J.D. (2002) from the College of William & Mary.


text:
Top Definition
A word used to describe frustration, shock, or questioning. Can be uttered in many tones. Can be synonymous with "What the heck?" or "Huh?"
Gina: A pickled stuffed matress. Kewl.
Sonia: Whay? Sleeping in a hammock mouthing the words to Eye of the Tiger?
Gina: WHAY??? ITS SO STUPID!
Sonia: Whay? Sleeping in a hammock mouthing the words to Eye of the Tiger?
Gina: WHAY??? ITS SO STUPID!
מאת AReallyMajesticLookingBeast 16 באוגוסט, 2009
Trending Now
Can you define these popular missing words?
Whay - Used when something funny or misfortunate for someone has happened. Commonly used in schools.
Teacher: Class, sit down now!
Pupil: No chance, Whay!
Pupils: Whaay!
Pupil: No chance, Whay!
Pupils: Whaay!
מאת Soothy 7 באוגוסט, 2008
Modification of "why?" used to indicate a particular tone of voice when communicating online. This is associated with blondes and can be best visualized with a cocked head and hair twirled around a pinky finger.
"so this guy walks into a bar--"
"wait whay?"
"wait whay?"
מאת junkyard prince 10 באוקטובר, 2003
the word "well hey" combined into two words. Formerly used by 2pac in his song "Changes."
"whay, that's the way it is."
מאת hgqp28ghpq2 1 ביולי, 2005


text:
|Electron Trapping by Molecular Vibration
|Wednesday, 27 April 2005 00:00
In photoelectron spectroscopy experiments performed at the ALS, a group of researchers has found that electronic transitions normally thought to be forbidden can in fact be excited in conjunction with certain types of molecular vibrations. Specifically, they found that when the symmetry of a linear triatomic molecule is broken by asymmetric vibrational modes, photoelectrons can become temporarily trapped by the molecule before ultimately escaping, giving rise to a broad feature in the photoelectron spectrum known as a shape resonance. This process represents a novel type of symmetry-breaking phenomenon that has not been observed previously but appears to be widespread. Such coupling between electronic motion and nuclear motion becomes increasingly important as scientists learn more about the geometry and dynamics of novel chemical structures such as those found in nanodevices and transient chemical species, and the results have implications for studies that use photoelectron spectroscopy as a diagnostic tool.
The researchers performed vibrationally resolved photoelectron spectroscopy studies of gas-phase carbon disulfide (CS2), a simple molecule consisting of a central carbon atom with two sulfur atoms on each side, 180 degrees apart. This molecule has one "bending" vibrational mode and two "stretching" modes: one symmetric and one antisymmetric.
Using the High-Resolution Atomic and Molecular Electron Spectrometer (HiRAMES) endstation at ALS Beamline 10.0.1, the group investigated how the vibrational structure in the photoelectron spectrum changes as the incident photon energy is varied. They found that when the incident photon energy is tuned to the shape resonance (about 40 eV), the peaks corresponding to the bending and asymmetric stretch modes are dramatically enhanced.
This is a new resonance phenomenon: the observed shape resonance is the result of coupling between vibrational modes and electronic transitions that are "forbidden" by selection rules. However, such rules are based on simplifying approximations, and nominally forbidden behavior can occur as the result of unanticipated processes. Thus, exceptions to the rules provide opportunities to gain deeper insight into how electronic motion and nuclear motion are intertwined. In the case of CS2, the forbidden behavior is observed only when the photoelectrons are tuned to specific resonant energies and become trapped, or quasibound, when the molecule is distorted from its equilibrium geometry. This point is made dramatically clear in plots of the relative probabilities (branching ratios) of the various vibrational modes vs. incident photon energy. The resonance peak appears vividly for the two asymmetric vibrations but is absent in the plot for the symmetric vibrational mode.
In addition, the researchers note that the shape and width of the curves for the bending mode and the antisymmetric stretching mode are very similar; only their amplitudes are different. This indicates that the resonance trapping does not depend on the specific type of distortion in the molecular geometry, only on the fact that the motion breaks the molecule's symmetry. The researchers have found that this type of unprecedented behavior is exhibited for other molecules and is likely to be a general phenomenon. In addition to these experimental results, they have performed accurate electron-molecule scattering calculations, and these theoretical results were largely responsible for the qualitative explanations provided here.
The results demonstrate that there are resonances with little sensitivity to distortions in bond length. Because it is common to correlate shape resonance position with changes in bond length, this has implications for studies that use vacuum ultraviolet or x-ray probes for analyzing complex or exotic structures. More generally, the results provide a natural means of examining coupling between nuclear and electronic degrees of freedom and for developing tools based on the connections between them.
Research conducted by Jeff Rathbone and Erwin Poliakoff (Louisiana State University); John Bozek (ALS); and Robert Lucchese (Texas A&M University).
Research funding: U.S. Department of Energy, Office of Basic Energy Sciences (BES), Chemical Sciences, Geosciences, and Biosciences Division; the Robert A. Welch Foundation; and the Texas A&M University Supercomputing Facility. Operation of the ALS is supported by BES.
Publication about this research: G.J. Rathbone, E.D. Poliakoff, J.D. Bozek, and R.R. Lucchese, "Observation of the symmetry-forbidden 5σu→ kσu CS2 transition: A vibrationally driven photoionization resonance," Phys. Rev. Lett. 92, 143002 (2004).